CN1555387A - Polymeric compositions for forming optical waveguides, optical waveguides formed therefrom, and methods for making same - Google Patents

Abstract

The present invention relates to polymer compositions and methods of polymerizing such compositions. Furthermore, the present invention relates to polymer compositions that are useful in forming waveguides and to methods for making waveguides using such polymer compositions.

Description

Polymer composition for manufacturing optical waveguide, optical waveguide manufactured thereby, and method for manufacturing the waveguide

Information on related applications

This application claims priority to previously filed U.S. provisional application 60/221,420, filed on 28/7/2000, entitled "Polymeric Compositions for forming optical Waveguides; optical Waveguides Formed thermally from; and methods for marking Same ", and claim priority to U.S. provisional application 60/252,251, filed on 21/11/2000, entitled" Polymeric compositions for Forming Optical Waveguides; optical Waveguides FormedTheefrom; and Methods for Making Same ", both of which are incorporated herein by reference in their entirety.

Technical Field

The invention described herein relates generally to polymer compositions for making optical waveguides and methods for making such optical waveguides from the same. In particular, the invention relates to polymers prepared from at least one cycloolefin monomer, which can be used for the construction of optical waveguides by the clad-first or corefirst technology.

Background

The continuing demand for increased transmission rates, information capacity, and data density in integrated optical and optoelectronic (device) circuits has become an motivating force behind many innovations in the areas of broadband communications, high-capacity information storage, and large-screen and portable information displays. Although glass optical fibers are routinely used for remote high-speed data transmission, they are inconvenient for complex, high-density lines because of their high density, poor durability, and high expense in manufacturing complex optical circuits. Thus, there is a great desire for polymeric materials to build cost-effective, reliable, and passive and active integrated components that can perform the functions required for integrated optics.

Brief description of the invention

The present invention relates generally to polymer compositions for making optical waveguides and methods for making such optical waveguides from the same. In particular, the present invention relates to polymers prepared from at least one cycloolefin monomer, which polymers are useful for constructing optical waveguides by either clad-first or core-first techniques.

In certain embodiments, the present invention relates to polycyclic polymer compositions formed from one or more monomers or oligomers represented by the following structure:

wherein each X' independently represents oxygen, nitrogen, sulfur or a compound of the formula- (CH)₂)_n′-methylene, wherein n' is an integer from 1 to 5; "a" represents a single or double bond; r¹～R⁴Independently represents hydrogen, a hydrocarbyl group or a functional substituent; m is an integer of 0 to 5, with the proviso that when "a" is a double bond, R¹、R²One and R³、R⁴One of which is not present.

In another embodiment, R¹～R⁴Independently comprise a hydrocarbyl, halogenated hydrocarbyl or perhalogenated hydrocarbyl group selected from: i) linear or branched C₁～C₁₀An alkyl group; ii) linear or branched C₂～C₁₀An alkenyl group; iii) Linear or branched C₂～C₁₀An alkynyl group; iv) C₄～C₁₂A cycloalkyl group; v) C₄～C₁₂CycloalkenesA group; vi) C₆～C₁₂An aryl group; and vii) C₇～C₂₄Aralkyl, provided that R is¹～R⁴At least one of which is a hydrocarbyl group.

In another embodiment, R¹～R⁴One or more of which represent functional substituents independently selected from

-(CH₂)_n-CH(CF₃)₂-O-Si(Me)₃，-(CH₂)_n-CH(CF₃)₂-O-CH₂-O-CH₃，-(CH₂)_n-CH(CF₃)₂-O-C(O)-O-C(CH₃)₃，-(CH₂)_n-C(CF₃)₂-OH，-(CH₂)_nC(O)NH₂，-(CH₂)_nC(O)Cl，-(CH₂)_nC(O)OR⁵，-(CH₂)_n-OR⁵，-(CH₂)_n-OC(O)R⁵，-(CH₂)_n-C(O)R⁵，-(CH₂)_n-OC(O)OR⁵，-(CH₂)_nSi(R⁵)₃，-(CH₂)_nSi(OR⁵)₃，-(CH₂)_n-O-Si(R⁵)₃And- (CH)₂)_nC(O)OR⁶，

Wherein n independently represents an integer of 0 to 10, R⁵Independently represent hydrogen, linear or branched C₁～C₂₀Alkyl, linear or branched C₁～C₂₀Halogenated or perhalogenated alkyl, linear or branched C₂～C₁₀Alkenyl, linear or branched C₂～C₁₀Alkynyl, C₅～C₁₂Cycloalkyl radical, C₆～C₁₄Aryl radical, C₆～C₁₄Halogenated or perhalogenated aryl and C₇～C₂₄Aralkyl group; r⁶Is selected from-C (CH)₃)₃、-Si(CH₃)₃、-CH(R⁷)OCH₂CH₃、-CH(R⁷)OC(CH₃)₃Or one of the following cyclic groups:

or one of the following:

and

wherein R is⁷Represents hydrogen or linear or branched (C)₁～C₅) An alkyl group.

In another embodiment, a polymer composition according to the present invention is prepared from one or more monomers or oligomers described herein in combination with one or more crosslinking agents. Furthermore, in yet another embodiment, the one or more crosslinking agents are latent crosslinking agents.

In another embodiment, the at least one cross-linking agent may be a compound shown below:

in yet another embodiment, the one or more crosslinking agents are represented by one or more of the following structures:

and

in another embodiment, the invention relates to polycyclic polymer compositions prepared from one or more monomers or oligomers represented by the following structure:

wherein each X' independently represents oxygen, nitrogen, sulfur or a compound of the formula- (CH)₂)_n′-methylene, wherein n' is an integer from 1 to 5; q represents an oxygen atom or a group N (R)⁸)；R⁸Selected from hydrogen, halogen, straight or branched C₁～C₁₀Alkyl and C₆～C₁₈Aryl, m is 0 &And 5 is an integer.

In yet another embodiment, a polycyclic polymer composition is prepared from one or more monomers represented by the following structure:

wherein X' "represents oxygen, nitrogen, sulfur or has the formula- (CH)₂)_n′-methylene, wherein n' is an integer from 1 to 5; r^DIs deuterium, "i" is an integer of 0 to 6, with the proviso that when "i" is 0, R^1DAnd R^2DMust be present; r¹And R²Independently represents hydrogen, a hydrocarbyl group or a functional substituent; r^1DAnd R^2DWhich are optional and independently represent a deuterium atom or a deuterium-enriched hydrocarbon group containing at least one deuterium atom.

In another embodiment, the polymer composition for the waveguide is prepared from said one or several monomers or oligomers.

In a further embodiment, the polymer composition according to the invention also contains at least one crosslinking agent. In certain embodiments, the crosslinking agent is a latent crosslinking agent.

An advantage of the present invention is that it provides a polymer composition that allows for the manufacture of optical waveguides with better performance, such as a difference in refractive index of the core material over a wide wavelength range (e.g., about 400 to about 1600nm) (Δ n) of at least 0.00075 (i.e., at least 0.05% when the cladding material has a refractive index of about 1.5); lower intrinsic optical loss (less than about 1dB/cm and in some cases less than 0.5 dB/cm); a high glass transition temperature (Tg) (e.g., in one embodiment at least about 150 ℃, in another embodiment at least about 250 ℃, and in some cases at least about 280 ℃).

Furthermore, it is an advantage of the present invention that it provides a core and/or cladding composition that may have a low viscosity, such that it may be delivered for use in any suitable technology, including an ink jet printer, a screen printer, or a stencil printer. Furthermore, the core-first method for fabricating an optical waveguide as described in the disclosure is advantageous in that it allows the fabrication of optical waveguides that reduce and/or eliminate interlayer expansion phenomena (see fig. 5A and 5B for a photographic depiction of "expansion"). Thus, the core-first approach allows for the fabrication of improved waveguides.

The foregoing and other features of the invention are hereinafter fully described and particularly pointed out in the claims, the following description and the annexed drawings setting forth in detail one or more illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the invention may be employed.

Brief Description of Drawings

FIG. 1 is a diagram of the steps in a method of fabricating a clad-first waveguide;

FIGS. 2A-2C depict structures of waveguides fabricated using the deadd-first method of FIG. 1;

FIG. 3 is a process diagram of the core-first waveguide fabrication method of the present invention;

FIGS. 4A-4D are another set of waveguides fabricated using the core-first method of the present invention;

FIGS. 5A-5B are photographs comparing the manufacture of the clad-first waveguide of FIG. 1 with the manufacture of the core-first waveguide of FIG. 3;

FIG. 6 is a process diagram of the improved core-first waveguide fabrication method of the present invention;

FIGS. 7A-7B are optical micrographs illustrating waveguides fabricated by the methods of FIGS. 3 and 6, respectively;

FIG. 8 is a step diagram of a method of fabricating an isolated buried channel waveguide by cutting a multilayer film; and

fig. 9A to 9D illustrate the structure of a waveguide manufactured by the multilayer method of the present invention.

Detailed Description

As described above, the present invention relates to various methods that may be used to fabricate optical waveguides, and more particularly, to methods that may be used to fabricate optical waveguides having buried channels. Also, the present invention relates to compositions useful for making optical waveguides.

It should be noted that in the following and in the claims, range and ratio limits and/or range and time limits may be combined. Furthermore, as the terms are used throughout the patent specification and claims, the core composition and the coating composition (or coating) are defined to mean one of the following meanings:

(1) a composition comprising at least one monomer;

(2) a composition comprising at least one monomer and at least one oligomer, wherein the total amount of reactive monomers and/or reactive oligomers is at least about 30 weight percent based on the total weight of the core or coating composition;

(3) a composition comprising at least one monomer and at least one polymer, wherein the total amount of reactive monomers is at least about 30 weight percent based on the total weight of the core or cladding composition; and

(4) a composition comprising at least one monomer, at least one oligomer, and at least one polymer, wherein the total amount of reactive monomers and/or reactive oligomers is at least about 30 weight percent based on the total weight of the core or coating composition. Oligomers, as used throughout the specification and claims, are defined to mean compositions containing less than about 1000 of a given monomeric repeat unit.

Furthermore, the refractive indices mentioned here were determined at 589nm using an Abbe refractometer and/or at 633nm, 830nm and 1550nm using a Metricon Model 2010 prism coupler, according to the ASTM Designation # D542-95 standard.

In general, optical waveguides and buried channel optical waveguides include a core layer of a first refractive index and a cladding layer of a second refractive index, where the core layer is at least partially surrounded by the cladding layer. In another embodiment, the core layer is completely surrounded by cladding (i.e., buried channel structure or three-layer optical waveguide). It is the core that transmits the light and the cladding that encloses the light. In the case where the optical waveguide is a two-layer structure, the core layer is partially bound by an air layer.

From the above point of view, explicit expressions for the core and cladding will be discussed below. However, it is generally believed that the process disclosed below will work with any suitable polymer, provided that the resulting core and cladding meet the desired performance criteria for use with a waveguide. There are a number of waveguide performance criteria and table 1 summarizes the typical minimum performance criteria applicable to all waveguides, regardless of the field in which the waveguide is used. It should be noted, however, that the present invention is not so limited. Rather, other performance criteria may be obtained based on the polymer used.

TABLE 1
			Performance criteria	Minimum requirements	Nuclei Using embodiment CL5 Heart composition and embodiment CO1 Of the coating composition Comparative Performance of catheters
Refraction at 830nm Rate Deltan (core-cladding)	At least about 0.00075 (phase) When the content is 0.05%, wherein cover The refractive index of the layer is about 1.5)	About 0.03 (about 2.0%; coating thereof) Layer refractive index of about 1.5)
			Over a wide temperature range Δ n is uniform	About 0 to 40 DEG C	0～175℃
Intrinsic optical loss	Less than about 1dB/cm	Less than about 0.1dB/cm (at 515 to 870nm position)
			Waveguide transmission loss	Less than about 1dB/cm	About 0.14dB/cm
Birefringence, in-plane Out-of-plane (Δ n)	Less than about 10-2Less than about 10-2	Less than about 10-5Less than about 10-3
			At 125 deg.C in air Has an oxidation stability of 2000 hours	At 125 deg.C at least 500 hr Time of flight	At 125 deg.C for at least 2200 hr
Compatibility with solder reflow Minimum vitrification of Temperature change (Tg)	A Tg of at least 150 DEG C	A Tg of at least 250 DEG C
			Low moisture absorption	Less than 3 percent	Less than 0.3 percent
Due to mechanical strength Minimum elongation	At least about 5%	At least about 10%

In certain embodiments, the waveguides can be fabricated from a variety of polymer compounds including, but not limited to, polyacrylates (such as deuterated polyfluoromethylacrylates), polyimides (such as cross-linked polyimides or fluorinated polyimides), benzocyclobutenes, or fluorobenzocyclobutenes by the methods discussed below.

In another embodiment, the waveguides of the invention are made with polymers prepared from cyclic olefin monomers. In yet another embodiment, the cyclic olefin monomer used to prepare the waveguide polymer is a norbornene-type monomer.

Preparation of cycloolefin Polymer:

in general, the polymerization of the cycloolefins used in certain embodiments of the invention, in certain embodiments, is carried out by addition polymerization using group 10 metal complexes, resulting in saturated polymers having high glass transition temperatures. In another embodiment, the polymerization of the cycloalkenes used in one embodiment of the invention is carried out using a group 10 metal complex and a weakly coordinating counter anion.

In another embodiment, the cyclic olefin is polymerized by contacting the polymerizable polycycloolefin monomer starting material with a high activity catalyst system comprising a group 10 metal cation complex and a weakly coordinating counteranion complex having the formula:

[(R’)_zM(L’)_x(L”)_y]_b[WCA]_d，

wherein M represents a group 10 transition metal; r' represents an anionic hydrocarbyl group containing a ligand; l' represents a group 15 neutral electron donor ligand; l' represents a labile neutral electron donor ligand; z is 0 or 1; x is 1 or 2; y is 0, 1, 2 or 3 and the sum of x, y and z is 4; b and d are numbers representing multiples of the cationic complex and weakly coordinating counteranion complex (WCA), respectively, to balance the charge of the overall catalyst complex. The monomer feed may be neat or dissolved in solution and contacted with a catalyst having the formula described above. Alternatively, the catalyst may be prepared in situ, i.e. by mixing the monomeric starting components to form the components of the catalyst.

Catalyst system

The catalyst of the present invention comprises a group 10 metal cation complex and a weakly coordinating counteranion complex represented by the following formula I:

[(R’)_zM(L’)_x(L”)_y]_b[WCA]_dI

wherein M represents a group 10 transition metal; r' represents an anionic hydrocarbyl ligand; l' represents a group 15 neutral electron donor ligand; l' represents a labile neutral electron donor ligand; x is 1 or 2; y is 0, 1, 2 or 3, wherein the sum of x, y and z is 4; b and d are numbers representing multiples of the cationic complex and weakly coordinating counteranion complex (WCA), respectively, to balance the charge of the overall catalyst complex.

A weakly coordinating counteranion complex is an anion that is only weakly coordinated to a cation complex. It is sufficiently labile to be displaced by a neutral lewis base, solvent or monomer. More specifically, the WCA anion functions as a cation complex stabilizing anion which does not transfer to the cation complex to form a neutral product. The WCA anion is relatively inert under non-oxidizing, non-reducing and non-nucleophilic conditions.

An anionic hydrocarbyl ligand is any hydrocarbyl ligand which, when removed from the metal center M in its closed electronic structure, has a negative charge.

A neutral electron donor ligand is any ligand that, when removed from the metal center M in its closed electronic structure, has a neutral charge.

A labile neutral electron donor ligand is any ligand that is not strongly bound to metal center M, is easily displaced, and has a neutral charge when removed from metal center M in its closed electronic structure.

In the above cationic complex, M represents a group 10 metal selected from nickel and palladium. In another embodiment, M represents platinum.

Representative ligand-containing anionic hydrocarbyl radicals R' include hydrogen, linear or branched C₁～C₂₀Alkyl radical, C₅～C₁₀Cycloalkyl, linear or branched C₂～C₂₀Alkenyl radical, C₆～C₁₅Cycloalkenyl, allyl ligands or canonical forms thereof, C₆～C₃₀Aryl radical, C₆～C₃₀A hetero atom of aryl, and C₇～C₃₀Aralkyl, each of which may be optionally substituted with hydrocarbyl and/or heteroatom substituents selected from linear or branched C in one embodiment₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, threadLinear or branched C₂～C₅Alkenyl, linear or branched C₂～C₅Haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus and optionally linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl and halogen-substituted phenyl, R' also represents an anionic hydrocarbyl radical of the formula R "C (O) O, R" OC (O) CHC (O) R ", R" C (O) S, R "C (S) O, R" C (S) S, R "O, R"₂N, wherein R 'is the same as R' immediately above defined.

The aforementioned cycloalkyl and cycloalkenyl ligands can be monocyclic or polycyclic. The aryl ligands can be monocyclic (e.g., phenyl) or fused ring systems (e.g., naphthyl). In addition, any of the cycloalkyl, cycloalkenyl and aryl groups can together form a fused ring system. Any of the above monocyclic, polycyclic and aromatic ring systems may optionally be mono-or polysubstituted, the substituents being independently selected from hydrogen, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy, halogen chlorine, fluorine, iodine and bromine, C₅～C₁₀Cycloalkyl radical, C₆～C₁₅Cycloalkenyl radical and C₆～C₃₀And (4) an aryl group. An example of a multicyclic alkyl moiety is norbornyl ligand. An example of a polycycloalkenyl moiety is a norbornenyl ligand. Examples of aryl ligand groups include phenyl and naphthyl. To illustrate, structure I below represents a cationic complex wherein R' is a cycloalkenyl ligand derived from 1, 5-cyclooctadiene. Structures II and III illustrate cationic complexes in which R' represents polycycloalkyl and polycycloalkenyl ligands, respectively. In Structure III, the norbornenyl ligand is an alkeneAnd (4) substituting the group.

Structure I structure II

Structure III

Wherein M, L', L ", x and y are as previously defined.

Additional examples of cationic complexes, wherein R' represents a ring system, are illustrated in structures IV-IVc below.

Structure IV structure IVa structure IVb structure IVc

Wherein M, L', L ", x and y are as previously defined.

In another embodiment of the invention, R' represents a hydrocarbyl ligand containing a terminal group that coordinates to the group 10 metal. formula-C for hydrocarbyl ligands containing terminal coordinating groups_d’H_2d’X → wherein d' represents the number of carbon atoms in the hydrocarbon group main chain and is an integer of 3 to 10, and X → represents an alkenyl group or a heteroatom-containing moiety coordinated to the group 10 metal center. The ligand forms a metallocycle or heteroatom-containing metallocycle with the group 10 metal. Any hydrogen atom on the hydrocarbyl backbone of the above formula may be independently substituted with a substituent selected from R^1’、R^2’And R^3’They areAs defined below.

The entity of the hydrocarbyl metallocycle cation complex having a terminal coordinating group is represented by structure V, as schematically shown below:

structure V

Wherein M, L ', L ", d', X and y are as defined above and X represents a group selected from-CHR^4’＝CHR^4’、-OR^4’、-SR^4’、-N(R^4’)₂、-N＝NR^4’、-P(R^4’)₂、-C(O)R^4’、-C(R^4’)＝NR^4’、-C(O)OR^4’、-OC(O)OR^4’、-OC(OR^4’) And R is^4’Represents hydrogen, halogen, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, C₅～C₁₀Cycloalkyl, linear or branched C₂～C₅Alkenyl, linear or branched C₂～C₅Haloalkenyl, substituted or unsubstituted C₆～C₁₈Aryl and substituted or unsubstituted C₇～C₂₄An aralkyl group.

The hydrocarbyl metallacycle with the substituted end group may be represented by the following structure Va:

structure Va

Wherein M, L ', L', X, x and y are as defined above, n represents an integer of 0 to 8 and R is^1’、R^2’And R^3’Independently represent hydrogen, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₂～C₅Alkenyl, linear or branched C₂～C₅Haloalkenyl, substituted or unsubstituted C₆～C₃₀Aryl and substituted or unsubstituted C₇～C₃₀Aralkyl and halogen. R^1’、R^2’And R^3’Any of which may form, together with the carbon atoms to which they are attached, a substituted or unsubstituted aliphatic C₅～C₂₀Monocyclic or polycyclic systems, substituted or unsubstituted C₆～C₁₀Aromatic ring system, substituted or unsubstituted C₁₀～C₂₀Fused aromatic ring systems and combinations thereof. When substituted, the above rings may contain mono-or polysubstitution, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, halogen, linear or branched C₁～C₅Alkoxy, and halogen is selected from chlorine, fluorine, iodine, and bromine. In the above structure Va, it should be noted that when n is 0, X is bonded to R containing a carbon atom^2’SubstitutionThe carbon atoms in the radicals are bonded.

Representative terminal group-containing hydrocarbyl metallocycle cationic complexes, wherein the substituents together represent aromatic and aliphatic ring systems, are illustrated in structures Vb and Vc below.

Structure Vb structure Vc

Additional examples of terminal group-containing hydrocarbyl metallocycle cation complexes are shown in the following structures Vd through Vg, where R is^1’～R^3’Any of which may together form an aromatic ring system.

Structure Vd structure Ve structure Vf structure Vg

Illustrative examples of cationic complexes containing polycyclic aliphatic ring systems are shown in the following structures Vh, Vi and Vj:

structure Vh constructs Vi structure Vj

In the above structures V to Vj, n' is an integer of 0 to 5; m, L ', L', X, n, X, y, R^1’And R^4’As defined above, "a" represents a single or double bond, R^5’And R^6’Independently represent hydrogen, linear or branched C₁～C₁₀Alkyl radical, R^5’And R^6’Together with the carbon atoms to which they are attached, form saturated and unsaturated cyclic groups containing from 5 to 15 carbon atoms.

Examples of heteroatom-containing aryl ligands R' are pyridyl and quinolyl ligands.

The allyl ligand in the cationic complex can be represented by the following structure:

structure VI

Wherein R is^20’、R^21’And R^22’Each independently represents hydrogen, halogen, linear or branched C₁～C₅Alkyl radical, C₅～C₁₀Cycloalkyl, linear or branched C₂～C₅Alkenyl radical, C₆～C₃₀Aryl radical, C₇～C₃₀Aralkyl, each of which is optionally substituted with a substituent selected from linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, halogen and C which may optionally be linear or branched₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl and phenyl substituted by halogen. R^20’、R^21’And R^22’Any two of which may be joined to the carbon atom to which they are attached to form a ring or polycyclic ring, may optionally be linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Examples of suitable allyl ligands in the cationic complexes of the present invention include, but are not limited to, allyl, 2-chloroallyl, crotyl, 1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, and β -pinenyl.

Representative cationic complexes containing allyl ligands are shown below.

Structure VIa structure VIb

In structures VI, VIa, and VIb, M, L', L ", x, and y are as previously defined.

Examples of other allyl ligands can be found in the following documents:

R.G.Guy and

L.Shaw, Advances in organic Chemistry and Radiochemistry, Vol.4, Academic Press Inc., New York, 1962, J.Birmingham, E.de Boer, M.L.H.Green, R.B.King, R.K ö ster, P.L.I.Nagy, G.N.Schrauzer, Advances in organometallic Chemistry, Vol.2, Academic Press Inc., New York, 1964, W.T.Dent, R.Long and A.J.Wilkinson, J.Chem.Soc., 1964)1585, and H.C.Volger, Rec.Trav.m.Pay.88 Bas 225;

all of which are incorporated herein by reference.

Representative neutral electron donor ligands L' include amines, pyridines, organic phosphorus-containing compounds and arsines and stibine (tri) hydrogens, of the formula:

E(R^7’)₃

wherein E is arsenic or antimony, R^7’Independently selected from hydrogen, linear or branched C₁～C₁₀Alkyl radical, C₅～C₁₀Cycloalkyl, linear or branched C₁～C₁₀Alkoxy, allyl, linear or branched C₂～C₁₀Alkenyl radical, C₆～C₁₂Aryl radical, C₆～C₁₂Aryloxy radical, C₆～C₁₂Aryl sulfides (e.g. PhS), C₇～C₁₈Aralkyl, cyclic ether and thioether, tri (linear or branched C)₁～C₁₀Alkyl) silyl, tri (C)₆～C₁₂Aryl) silyl, tri (linear or branched C)₁～C₁₀Alkoxy) silyl, triaryloxysilyl, tris (linear or branched C)₁～C₁₀Alkyl) siloxy and tri (C)₆～C₁₂Aryl) siloxy, each of the aforementioned substituents being optionally substituted by a linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, C₁～C₅Alkoxy, halogen, and combinations thereof. Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butylAlkyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl. Representative cycloalkyl groups include, but are not limited to, cyclopentyl and cyclohexyl. Substitute for Chinese traditional medicineRepresentative alkoxy groups include, but are not limited to, methoxy, ethoxy, and isopropoxy. Representative cyclic ether and cyclic thioether groups include, but are not limited to, furyl and thienyl, respectively. Representative aryl groups include, but are not limited to, phenyl, o-tolyl, and naphthyl. Representative aralkyl groups include, but are not limited to, benzyl and phenethyl (i.e., -CH)₂CH₂PH). Representative silyl groups include, but are not limited to, triphenylsilyl, trimethylsilyl, and triethylsilyl. In the general definition given above, each of the aforementioned groups may optionally be linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl and halogen.

Representative pyridines include lutidine (including 2, 3-; 2, 4-; 2, 5-; 2, 6-; 3, 4-; and 3, 5-substituted), picoline (including 2-, 3-, or 4-substituted), 2, 6-di-tert-butylpyridine, and 2, 4-di-tert-butylpyridine.

Representative arsines include triphenylarsine, triethylarsine, and triethoxysilylarsine.

Representative stibated (tri) hydrogens include triphenylstibated (tri) hydrogen and tritylthiostibated (tri) hydrogen.

Suitable amine ligands may be selected from the formula N (R)^8’)₃Wherein R is^8’Independently represent hydrogen, linear or branched C₁～C₂₀Alkyl, linear or branched C₁～C₂₀Haloalkyl, substituted or unsubstituted C₃～C₂₀Cycloalkyl, substituted or unsubstituted C₆～C₁₈Aryl and substituted or unsubstituted C₇～C₁₈An aralkyl group. When substituted, the cycloalkyl, aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₁₂Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy radical, C₆～C₁₂Aryl, and a halogen selected from chlorine, bromine, and fluorine. Representative amines include, but are not limited to, ethylamine, triethylamine, diisopropylamine, tributylamine, N-dimethylaniline, N-dimethyl-4-t-butylaniline, N-dimethyl-4-t-octylaniline, and N, N-dimethyl-4-hexadecylaniline.

Organophosphorus-containing ligands include phosphines, phosphites, phosphonites, phosphonates, having the formula P (R)^7’)_g[X’(R^7’)_h]_3-gWherein X' is oxygen, nitrogen or silicon, R^7’Same as defined above and each R^7’The substituents are independent of the other R^7’A substituent, g is 0, 1, 2, or 3, and h is 1, 2, or 3, with the proviso that when X ' is a silicon atom, h is 3, when X ' is an oxygen atom, h is 1, and when X ' is a nitrogen atom, h is 2. When g is 0 and X' is oxygen, any two or 3R^7’May form a cyclic moiety together with the oxygen atom to which they are attached. When g is 3, any two R^7’May form a phosphacycle with the phosphorus atom to which they are attached, of the formula:

wherein R is^7’The same as defined above and h' is an integer of 4 to 11.

The organophosphorus compounds may also include bidentate phosphine ligands of the formula:

wherein R is^7’The same as defined above and it is also contemplated herein that i is 0, 1, 2, or 3.

Representative phosphine ligands include, but are not limited to, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tricyclopentylphosphine, triallylphosphine, tricyclohexylphosphine, triphenylphosphine, trinaphthylphosphine, tri-p-tolylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tritylphosphine, tris (p-trifluoromethylphenyl) phosphine, tris (trifluoromethyl) phosphine, tris (p-fluorophenyl) phosphine, tris (p-trifluoromethylphenyl) phosphine, allylbiphenylphosphine, benzylbiphenylphosphine, bis (2-furanyl) phosphine, bis (4-methoxyphenyl) phenylphosphine, bis (4-methylphenyl) phosphine, bis (3, 5-bis (trifluoromethyl) phenyl) phosphine, tert-butylbis (trimethylsilyl) phosphine, tris (tert-butyl) phosphine, tris (trifluoromethyl) phosphine, tris (p-tolyl) phosphine, tris (p, Tert-butylbiphenylphosphine, cyclohexylbiphenylphosphine, diallylphenylphosphine, diphenylmethylphosphine, dibutylphenylphosphine, dibutylphosphine, di-tert-butylphosphine, dicyclohexylphosphine, diethylphenylphosphine, diisobutylphosphine, dimethylphenylphosphine, dimethyl (trimethylsilyl) phosphine, biphenylphosphine, biphenylpropylphosphine, biphenyl (p-tolyl) phosphine, biphenyl (trimethylsilyl) phosphine, biphenylvinylphosphine, divinylphenylphosphine, ethylbiphenylphosphine, (2-methoxyphenyl) methylphenylphosphine, tri-n-octylphosphine, tris (3, 5-bis (trifluoromethyl) phenyl) phosphine, tris (3-chlorophenyl) phosphine, tris (4-chlorophenyl) phosphine, tris (2, 6-dimethoxyphenyl) phosphine, tris (3-fluorophenyl) phosphine, tris (2-furyl) phosphine, di-butylphosphine, di-tert-butylphosphine, dicyclohexylphosphine, diethylphenylphosphine, Tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (3-methoxypropyl) phosphine, tris (2-thienyl) phosphine, tris (2, 4, 6-trimethylphenyl) phosphine, tris (trimethylsilyl) phosphine, isopropylbiphenylphosphine, dicyclohexylphenylphosphine, (+) -neopentylbiphenylphosphine, tritylphosphine, biphenyl (2-methoxyphenyl) phosphine, biphenyl (pentafluorophenyl) phosphine, bis (pentafluorophenyl) phenylphosphine, and tris (pentafluorophenyl) phosphine.

Exemplary bidentate phosphine ligands include, but are not limited to, (R) - (+) -2, 2 '-bis (biphenylphosphino) -1, 1' -binaphthyl, bis (dicyclohexylphosphino) methane; di (dicyclohexylphosphino) ethane, di (biphenylphosphino) methane, di (biphenylphosphino) ethane.

The phosphine ligand may also be selected from water-soluble phosphine compounds, so that the resulting catalyst has solubility in aqueous media. Selected phosphines of this type include, but are not limited to, carboxy-substituted phosphines such as 4- (biphenylphosphine) benzoic acid and 2- (biphenylphosphine) benzoic acid, sodium 2- (dicyclohexylphosphino) ethanesulfonate, 4 ' - (phenylphosphino) bis (benzenesulphonic acid) dipotassium salt, 3 ' -phosphinidynetris (benzenesulphonic acid) trisodium salt, 4- (dicyclohexylphosphino) -1, 1-dimethylpiperidinium chloride, 4- (dicyclohexylphosphino) -1, 1-dimethylpiperidinium iodide, quaternary amine-functionalized salts of phosphines such as 2- (dicyclohexylphosphino) -N, N, N-trimethylacetamide chloride, 2 ' - (cyclohexylphosphino) bis [ N, N, N-trimethylacetamide ] dichloride, 2- (cyclohexylphosphino) bis [ N, N, N-trimethylacetamide ] dichloride, 2, 2' - (cyclohexylphosphinylene) bis [ [ N, N, N-trimethylacetamide ] diiodide and 2- (dicyclohexylphosphinyl) -N, N, N-trimethylacetamide iodide.

Examples of phosphite ligands include, but are not limited to, trimethyl phosphite, diethylphenyl phosphite, triethyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, tri-sec-butyl phosphite, triisobutyl phosphite, tri-t-butyl phosphite, dicyclohexyl phosphite, tricyclohexyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, tris (p-trifluoromethylphenyl) phosphite, benzyl diethyl phosphite, and trityl phosphite.

Examples of phosphonate ligands include, but are not limited to, methyl biphenyl phosphonate, ethyl biphenyl phosphonate, isopropyl biphenyl phosphonate, and phenyl biphenyl phosphonate.

Examples of phosphonite ligands include, but are not limited to, biphenylylphosphite, dimethylphenylphosphite, diethylmethylphosphonite, diisopropylphenylphosphonite, and diethylphenylphosphonite.

Representative labile neutral electron donor ligands (L') are reaction diluents, reaction monomers, DMF, DMSO, dienes, including C₄～C₁₀Aliphatic and C₄～C₁₀Representative of dienes are butadiene, 1, 6-hexadiene and Cyclooctadiene (COD), water, chloroalkanes, alcohols, ethers, ketones, nitriles, aromatic hydrocarbons, phosphine oxides, organic carbonates and esters.

Representative chloroalkanes include, but are not limited to, dichloromethane, 1, 2-dichloroethane, and carbon tetrachloride.

Suitable alcohol ligands may be selected from those having the formula R^9’Alcohols of OH, wherein R^9’Represents a linear or branched chainChain C₁～C₂₀Alkyl, linear or branched C₁～C₂₀Haloalkyl, substituted and unsubstituted C₃～C₂₀Cycloalkyl, substituted and unsubstituted C₆～C₁₈Aryl and substituted and unsubstituted C₇～C₁₈An aralkyl group. When substituted, the cycloalkyl, aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₁₂Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy radical, C₆～C₁₂Aryl, and a halogen selected from chlorine, bromine, and fluorine. Representative alcohols include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, butanol, hexanol, t-butanol, neopentyl glycol, phenol, 2, 6-diisopropylphenol, 4-t-octylphenol, 5-norbornene-2-methanol, and dodecanol.

Suitable ether ligands and thioether ligands may be selected from the group consisting of those having the formula (R)^10’-O-R^10’) And (R)^10’-S-R^10’) Ethers and thioethers of (2), wherein R^10’Independently represents a linear or branched C₁～C₁₀Alkyl, linear or branched C₁～C₂₀Haloalkyl, substituted and unsubstituted C₃～C₂₀Cycloalkyl, linear or branched C₁～C₂₀Alkoxy, substituted and unsubstituted C₆～C₁₈Aryl and substituted and unsubstituted C₆～C₁₈An aralkyl group. When substituted, the cycloalkyl, aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₁₂Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy radical, C₆～C₁₂Aryl, and a halogen selected from chlorine, bromine, and fluorine, together with the oxygen or sulfur atom to which they are attached, form a cyclic ether or cyclic thioether. Representative examplesEthers of (a) include, but are not limited to, dimethyl ether, dibutyl ether, methyl tert-butyl ether, diisopropyl ether, diethyl ether, dioctyl ether, 1, 4-dimethoxyethane, THF, 1, 4-dioxane, and tetrahydrothiophene.

Suitable ketone ligands are represented by the formula R^11’C(O)R^11’Is represented by the ketone (b) in which R is^11’Independently represent hydrogen, linear or branched C₁～C₂₀Alkyl, linear or branched C₁～C₂₀Haloalkyl, substituted and unsubstituted C₃～C₂₀Cycloalkyl, substituted and unsubstituted C₆～C₁₈Aryl and substituted and unsubstituted C₆～C₁₈An aralkyl group. When substituted, the cycloalkyl, aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₁₂Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy radical, C₆～C₁₂Aryl, and a halogen selected from chlorine, bromine, and fluorine. Representative ketones include, but are not limited to, acetone, methyl ethyl ketone, cyclohexanone, and benzophenone.

Nitrile ligands of the formula R^12’CN represents, wherein R^12’Represents hydrogen, linear or branched C₁～C₂₀Alkyl, linear or branched C₁～C₂₀Haloalkyl, substituted and unsubstituted C₃～C₂₀Cycloalkyl, substituted and unsubstituted C₆～C₁₈Aryl and substituted and unsubstituted C₆～C₁₈An aralkyl group. When substituted, the cycloalkyl, aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₁₂Alkyl, linear or branched C₁～C₅A halogenated alkyl group,Linear or branched C₁～C₅Alkoxy radical, C₆～C₁₂Aryl, and a halogen selected from chlorine, bromine, and fluorine. Representative nitriles include, but are not limited to, acetonitrile, propionitrile, benzonitrile, benzyl cyanide, and 5-norbornene-2-carbonitrile.

The arene ligands may be selected from substituted and unsubstituted C's containing mono-or polysubstitution₆～C₁₂Aromatic hydrocarbons in which the substituents are independently selected from hydrogen, linear or branched C₁～C₁₂Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy radical, C₆～C₁₂Aryl, and a halogen selected from chlorine, bromine, and fluorine. Representative aromatic hydrocarbons include, but are not limited to, toluene, benzene, o-, m-, and p-xylene, 1,3, 5-trimethylbenzene, fluoro (substituted) benzene, o-difluorobenzene, p-difluorobenzene, chlorobenzene, pentafluorobenzene, o-dichlorobenzene, and hexafluorobenzene.

Suitable trialkyl and triaryl phosphine oxide ligands can be used with the formula P (O) (R)^13’)₃Is represented by phosphine oxide of (a), wherein R^13’Independently represents a linear or branched C₁～C₂₀Alkyl, linear or branched C₁～C₂₀Haloalkyl, substituted and unsubstituted C₃～C₂₀Cycloalkyl, linear or branched C₁～C₂₀Alkoxy, linear or branched C₁～C₂₀Haloalkoxy, substituted and unsubstituted C₆～C₁₈Aryl and substituted and unsubstituted C₆～C₁₈An aralkyl group. When substituted, the cycloalkyl, aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₁₂Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy radical, C₆～C₁₂Aryl, and a halogen selected from chlorine, bromine, and fluorine. Representative phosphine oxides include, but are not limited to, triphenylphosphine oxide, tributylphosphine oxide, trioctylphosphine oxide, tributylphosphate, and tris (2-ethylhexyl) phosphate.

Representative carbonates include, but are not limited to, ethylene carbonate and propylene carbonate.

Representative esters include, but are not limited to, ethyl acetate and isoamyl acetate.

Description of WCA

A weakly coordinating counteranion complex, [ WCA ], having formula I, selected from borate and aluminate, phenylboronic anions, carborane and halocarborane anions.

The borate and aluminate weakly coordinating counter anions are represented by formulas II and III:

[M’(R^24’)(R^25’)(R^26’)(R^27’)]^-II

[M’(OR^28’)(OR^29’)(OR^30’)(OR^31’)]^- III

wherein in formula II, M' is boron or aluminum, R^24’、R^25’、R^26’And R^27’Independently represent fluorine, linear or branched C₁～C₁₀Alkyl, linear or branched C₁～C₁₀Alkoxy, linear or branched C₃～C₅Haloalkenyl, linear or branched C₃～C₁₂Trialkylsiloxy radical, C₁₈～C₃₆Triarylsiloxy, substituted and unsubstituted C₆～C₃₀Aryl and substituted and unsubstituted C₆～C₃₀Aryloxy group, wherein R^24’～R^27’Not all simultaneously represent alkoxy or aryloxy groups. When substituted, the aryl group may be mono-or polysubstituted, wherein the substituents are independently selected from linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy, linear or branched C₁～C₅Haloalkoxy, linear or branched C₁～C₁₂Trialkylsilyl group, C₆～C₁₈Triarylsilyl groups, and a halogen selected from chlorine, bromine, and fluorine. In another embodiment, the halogen is fluorine.

Representative borate anions of formula II include, but are not limited to, tetrakis (pentafluorophenyl) borate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, tetrakis (2-fluorophenyl) borate, tetrakis (3-fluorophenyl) borate, tetrakis (4-fluorophenyl) borate, tetrakis (3, 5-difluorophenyl) borate, tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate, tetrakis (3, 4,5, 6-tetrafluorophenyl) borate, tetrakis (3, 4, 5-trifluorophenyl) borate, methyltris (perfluorophenyl) borate, ethyltris (perfluorophenyl) borate, phenyltris (perfluorophenyl) borate, tetrakis (1, 2, 2-trifluorovinyl) borate, tetrakis (4-triisopropylsilyltetrafluorophenyl) borate, and mixtures thereof, Tetrakis (4-dimethyl-t-butylsilyltetrafluorophenyl) borate, (triphenylsilyloxy) tris (pentafluorophenyl) borate, (octyloxy) tris (pentafluorophenyl) borate, tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] phenyl ] borate, tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate, and tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate.

Representative aluminate anions of formula II include, but are not limited to, tetrakis (pentafluorophenyl) aluminate, tris (perfluorobiphenyl) fluoroaluminate, (octyloxy) tris (pentafluorophenyl) aluminate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate, and methyltris (pentafluorophenyl) aluminate.

In formula III, M' is boron or aluminum, R^28’、R^29’、R^30’And R^31’Independently represents a linear or branched C₁～C₁₀Alkyl, linear or branched C₁～C₁₀Haloalkyl, C₂～C₁₀Haloalkenyl, substituted and unsubstituted C₆～C₃₀Aryl and substituted and unsubstituted C₇～C₃₀Aralkyl subject to the provisos: r^28’～R^31’At least three of which must contain halogen-containing substituents. When substituted, the aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy, linear or branched C₁～C₁₀Haloalkoxy, and halogen selected from chlorine, bromine, and fluorine. In another embodiment, the halogen is fluorine. Group OR^28’And OR^29’May together form a chelate substitutionWith the radical-O-R^32’-O-represents, wherein an oxygen atom is bonded to M' and R^32’Is a divalent radical selected from the group consisting of substituted and unsubstituted C₆～C₃₀Aryl and substituted and unsubstituted C₇～C₃₀An aralkyl group. In certain embodiments, the oxygen atom is bonded directly to the aromatic ring in the ortho or meta orientation or through an alkyl group. When substituted, the aryl and aralkyl groups may be mono-or polysubstituted, wherein the substituents are independently selected from linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy, linear or branched C₁～C₁₀Haloalkoxy, and halogen selected from chlorine, bromine, and fluorine. In another embodiment, the halogen is fluorine. Divalent R^32’Representative structures of groups are shown below:

wherein R is^33’Independently represent hydrogen, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, and halogen selected from chlorine, bromine, and fluorine (in another embodiment, halogen is fluorine); r^34’May be monosubstituted or occur up to four times around each aromatic ring, depending on the available valences for each carbon atom on the ring, and R^34’Independently represent hydrogen, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy, linear or branched C₁～C₁₀Haloalkoxy, and a halogen selected from chlorine, bromine, and fluorine (in certain embodiments, halogen is fluorine); and n' independently represents an integer of 0 to 6. It should be noted that when n' is 0, the formula-O-R^32’Oxygen atoms in-O-with R^32’Carbon in a representative aromatic ringThe atoms are directly bonded. That is, the oxygen atom in the above formula of the divalent structure, when n' is 0, and methylene or substituted methylene, - (C (R)^33’)₂)_n”-, in one embodiment, on the ortho or meta aromatic ring. A representative formula is-O-R^32’Chelating groups for-O-include, but are not limited to, 2, 3, 4, 5-tetrafluorobenzenediolate (-OC)₆F₄O-), 2, 3, 4, 5-tetrachlorobenzenediol (-OC)₆Cl₄O-) and 2, 3, 4, 5-tetrabromobenzenediolate (-OC)₆Br₄O-) and bis (1, 1' -biphenylTetrafluorophenyl-2, 2' -biphenoxide group).

Representative borate and aluminate anions of formula III include, but are not limited to

[B(OC(CF₃)₃)₄]^-，[B(OC(CF₃)₂(CH₃))₄]^-，[B(OC(CF₃)₂H)₄]^-，[B(OC(CF₃)(CH₃)H)₄]^-，[Al(OC(CF₃)₂Ph)₄]^-，[B(OCH₂(CF₃)₂)₄]^-，[Al(OC(CF₃)₂C₆H₄CH₃)₄]^-，[Al(OC(CF₃)₃)₄]^-，[Al(OC(CF₃)(CH₃)H)₄]^-，[Al(OC(CF₃)₂H)₄]^-，[Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]^-，[Al(OC(CF₃)₂C₆H₄-4-t-butyl)₄]^-，[Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄，]^-，[Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄，]^-，[Al(OC(CF₃)₂C₆H₂-2，6-(CF₃)₂-4-Si-i-Pr₃)₄]^-，[Al(OC(CF₃)₂C₆H₃-3，5-(CF₃)₂)₄]^-，[Al(OC(CF₃)₂C₆H₂-2，4，6-(CF₃)₃)₄]^-，and[Al(OC(CF₃)₂C₆F₅)₄]^-.

The boratobenzene anion used as the weakly coordinating counter anion may be represented by the following formula IV:

wherein R is^34’Selected from the group consisting of fluoro, fluoro hydrocarbyl, perfluorocarbyl, and fluoro and perfluoro ethers. As the term is used herein and throughout the patent specification, the term halohydrocarbyl means a hydrocarbyl group such as alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl wherein at least one hydrogen atom is replaced by a halogen selected from chlorine, bromine, iodine and fluorine (e.g., haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, haloaryl and haloaralkyl). The term fluorohydrocarbyl means a hydrocarbyl group in which at least one hydrogen atom is replaced by fluorine. The degree of halogenation can be between at least one hydrogen atom being replaced by a halogen atom (e.g., monofluoromethyl) and full halogenation (perhalogenation) in which all hydrogen atoms on the hydrocarbon group are replaced by halogen atoms (e.g., perhalocarbyl groups such as trifluoromethyl (perfluoromethyl)). The fluorocarbon and perfluorocarbyl groups contain, in one embodiment, 1 to 24 carbon atoms. In another embodiment, the fluorocarbon group and perfluorocarbyl group have 1 to 12 carbon atoms. In yet another embodiment, the fluorocarbon and perfluorocarbon groups contain 6 carbon atoms and may be linear or branched, cyclic or aromatic. Fluorocarbon and perfluorocarbyl radicals include, but are not limited to, fluoro and perfluoro linear or branched C₁～C₂₄Alkyl, fluoro and perfluoro C₃～C₂₄Cycloalkyl, fluoro and perfluoro C₂～C₂₄Alkenyl, fluoro and perfluoro C₃～C₂₄Cycloalkenyl, fluoro and perfluoro C₆～C₂₄Aryl, fluoro and perfluoro C₇～C₂₄An aralkyl group.The substituents of fluoro-and perfluoro-carbyl ether are each represented by the formula- (CH)₂)_mOR^36’Or- (CF)₂)_mOR^36’Is represented by the formula (I) in which R^36’Is a fluoro or perfluoro carbyl group as defined above, and m is an integer of 0 to 5. It should be noted that when m is 0, the oxygen atom of the ether moiety is directly bonded to the boron atom in the boratabenzene ring.

In a certain embodiment, R^34’Radicals include those that are electron withdrawing in nature, for example, fluoro and perfluoro hydrocarbon radicals selected from trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, pentafluorophenyl and bis (3, 5-trifluoromethyl) phenyl.

R^35’Independently represent hydrogen, halogen, perfluorocarbyl and silylperfluorocarbyl groups, wherein perfluorocarbyl and silylperfluorocarbyl groups are as defined above. In certain embodiments, the halogen is fluorine. When R is^35’When halogen, perfluorocarbyl and/or silylperfluorocarbyl groups, these groups are, in one embodiment, ortho or para to the boron atom in the boratabenzene ring. In another embodiment, when R^35’When halogen, perfluorocarbyl and/or silylperfluorocarbyl groups, these groups are para to the boron atom in the boratabenzene ring.

Representative boratobenzene cyclic anions include, but are not limited to [1, 4-dihydro-4-methyl-1- (pentafluorophenyl) ] -2-borate, 4- (1, 1-dimethyl) -1, 2-dihydro-1- (pentafluorophenyl) -2-borate, 1-fluoro-1, 2-dihydro-4- (pentafluorophenyl) -2-borate, and 1- [3, 5-bis (trifluoromethyl) phenyl ] -1, 2-dihydro-4- (pentafluorophenyl) -2-borate.

Carborane and halocarborane anions useful as weakly coordinating counter anions include, but are not limited to

CB₁₁(CH₃)₁₂ ^-，CB₁₁H₁₂ ^-，

1-C₂H₅CB₁₁H₁₁ ^-，1-Ph₃SiCB₁₁H₁₁ ^-，1-CF₃CB₁₁H₁₁ ^-，12-BrCB₁₁H₁₁ ^-，12-BrCB₁₁H₁₁ ^-，7，12-Br₂CB₁₁H₁₀ ^-，12-ClCB₁₁H₁₁ ^-，7，12-Cl₂CB₁₁H₁₀ ^-，1-H-CB₁₁F₁₁ ^-，1-CH₃-CB₁₁F₁₁ ^-，1-CF₃-CB₁₁F₁₁ ^-，12-CB₁₁H₁₁F^-，7，12-CB₁₁H₁₁F₂ ^-，7，9，12-CB₁₁H₁₁F₃ ^-，CB₁₁H₆Br₆ ^-，6-CB₉H₉F^-，6，8-CB₉H₈F₂ ^-，6，7，8-CB₉H₇F₃ ^-，6，7，8，9-CB₉H₆F₄ ^-，2，6，7，8，9-CB₉H₅F₅ ^-，CB₉H₅Br₅ ^-，CB₁₁H₆Cl₆ ^-，CB₁₁H₆F₆ ^-，CB₁₁H₆F₆ ^-，CB₁₁H₆I₆ ^-，CB₁₁H₆Br₆ ^-，6，7，9，10，11，12-CB₁₁H₆F₆ ^-，2，6，7，8，9，10-CB₉H₅F₅ ^-，1-H-CB₉F₉ ^-，12-CB₁₁H₁₁(C₆H₅)^-，1-C₆F₅-CB₁₁H₅Br₆ ^-，CB₁₁Me₁₂ ^-，CB₁₁(CF₃)₁₂ ^-，Co(B₉C₂H₁₁)₂ ^-，CB₁₁(CH₃)₁₂ ^-，CB₁₁(C₄H₉)₁₂ ^-，CB₁₁(C₆H₁₃)₁₂ ^-，Co(C₂B₉H₁₁)₂ ^-，Co(Br₃C₂B₉H₈)₂ ^-

And dodecahydro-1-carbadodecaborate.

Preparation of the catalyst

The catalysts of formula I may be prepared as preformed one-component catalysts in a solvent or in situ by mixing the catalyst precursor components in the desired monomers and polymerizing them.

The one-component catalysts of formula I can be prepared by mixing the catalyst precursors in a suitable solvent, allowing the reaction to proceed under suitable temperature conditions, and isolating the catalyst product. In another embodiment, the group 10 metal procatalyst is mixed with the group 15 electron donor compound and/or the labile neutral electron donor compound in a suitable solvent and the salt of the weakly coordinating anion is mixed to produce the preformed catalyst complex of formula I above. In another embodiment, a group 10 metal procatalyst containing a group 15 electron donor ligand is mixed with a salt of a weakly coordinating anion in a suitable solvent to produce a preformed catalyst complex.

The catalyst preparation reaction is carried out in a solvent which is inert to the reaction conditions. Examples of solvents suitable for the catalyst preparation reaction include, but are not limited to, alkane and cycloalkane solvents such as pentane, hexane, heptane, and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methyl-propane and 1-chloropentane; ethers such as THF and diethyl ether; aromatic solvents such as benzene, xylene, toluene, 1,3, 5-trimethylbenzene, chlorobenzene, and o-dichlorobenzene; and halocarbon solvents such as Freon 112; and combinations thereof. In certain embodiments, the solvent includes, for example, benzene, fluorobenzene, o-difluorobenzene, p-difluorobenzene, pentafluorobenzene, hexafluorobenzene, o-dichlorobenzene, chlorobenzene, toluene, o-, m-, and p-xylenes, 1,3, 5-trimethylbenzene, cyclohexane, THF, and dichloromethane.

Suitable temperatures for carrying out the reaction range from about-80 ℃ to about 150 ℃. In another embodiment, the reaction is carried out at a temperature in the range of from about-30 ℃ to about 100 ℃. In yet another embodiment, the reaction is carried out at a temperature in the range of from about 0 ℃ to about 65 ℃. In another embodiment, the reaction is carried out at a temperature in the range of from about 10 ℃ to about 40 ℃. The pressure requirement is not critical but may depend on the boiling point of the solvent used, i.e. the pressure sufficient to keep the solvent in the liquid phase. The reaction time is not critical and can be in the range of several minutes to 48 hours. In certain embodiments, the reaction is carried out under an atmosphere of an inert gas such as nitrogen or argon.

The reaction is carried out by dissolving the procatalyst in a suitable solvent and mixing the appropriate ligand and salt of the desired weakly coordinating anion with the dissolved procatalyst and optionally heating the solution until the reaction is complete. The preformed single-component catalyst may be isolated or used directly by adding a portion of the preformed catalyst to the polymerization medium. Isolation of the product can be accomplished by standard procedures such as evaporation of the solvent, washing of the solid with a suitable solvent, and then recrystallization of the desired product. The molar proportions of the catalyst components used to prepare the preformed one-component catalysts of the present invention depend on the metals contained in the procatalyst component. In one embodiment, the molar ratio of procatalyst/group 15 electron donor component/WCA salt is from 1: 1 to 10: 1 to 100, and in another embodiment, the molar ratio of procatalyst/group 15 electron donor component/WCA salt is from 1: 1 to 5: 1 to 1: 20. In yet another embodiment, the molar ratio of procatalyst/group 15 electron donor component/WCA salt is from 1: 1 to 2: 1 to 5. In embodiments of the invention where the procatalyst is coordinated with a group 15 electron donor ligand and/or a labile neutral electron donor ligand, the molar ratio of procatalyst (based on metal content) to WCA salt is from 1: 1 to 100. In another embodiment, the ratio is from 1: 1 to 20, and in yet another embodiment, the ratio is from 1: 1 to 5.

In certain embodiments, of the formula [ R 'MA']₂Of group 10 goldThe procatalyst dimer is combined with a group 15 electron donor compound, (L'), and a salt of a suitable weakly coordinating anion in a suitable solvent to produce the one-component catalyst product shown in equation (1) below.

1.

Having the formula [ R 'MA']₂Suitable procatalyst dimers of (i) include, but are not limited to, the following compositions, (allyl) palladium trifluoroacetate dimer, (allyl) palladium chloride dimer, (crotyl) palladium chloride dimer, (allyl) palladium iodide dimer, (β -pinenyl) palladium chloride dimer, methallylpalladium chloride dimer, 1-dimethallylpalladium chloride dimer, and (allyl) palladium acetate dimer.

In another embodiment, having the formula [ R' M (L ")_yA’]With a group 15 electron donor compound, (L'), and a salt of a suitable weakly coordinating anion in a suitable solvent to produce the one-component catalyst product shown in equation (2) below.

2.

Representative of those having the formula [ R 'M (L')_yA’]The procatalyst of (a) includes, but is not limited to, (COD) (methyl) palladium chloride.

In still further embodiments, having the formula [ R 'M (L')_xA’]Group 10 metal coordination procatalysts containing a group 15 electron donor ligand (L') are mixed in a suitable solvent with a salt of a suitable weakly coordinating anion to produce the one-component catalyst product shown in equation (3) below.

3.

Having the formula [ R 'M (L')_xA’]Suitable procatalysts include, but are not limited to, the following compositions:

(allyl) palladium (tricyclohexylphosphine) chloride,

(allyl) palladium (tricyclohexylphosphine) trifluoromethanesulfonate,

(allyl) palladium (triisopropylphosphine) trifluoromethanesulfonate,

(allyl) palladium (tricyclopentylphosphine) trifluoromethanesulfonate,

(allyl) Palladium (Tricyclohexylphosphine) trifluoroacetate (also referred to herein as allyl Pd-PCy)₃TFA)，

(allyl) palladium (tri-o-tolylphosphine) chloride,

(allyl) palladium (tri-o-tolylphosphine) trifluoromethanesulfonate,

(allyl) palladium (tri-o-tolylphosphine) nitrate,

(allyl) palladium (tri-o-tolylphosphine) acetate,

(allyl) palladium (triisopropylphosphine) bistrifluoromethanesulfonimide,

(allyl) palladium (tricyclohexylphosphine) bistrifluoromethanesulfonimide,

(allyl) palladium (triphenylphosphine) bistrifluoromethanesulfonimide,

(allyl) palladium (trinaphthylphosphine) trifluoromethanesulfonate,

(allyl) Palladium (Tricyclohexylphosphine) p-tolyl sulfonate

(allyl) palladium (triphenylphosphine) trifluoromethanesulfonate,

(allyl) palladium (triisopropylphosphine) trifluoroacetate,

(allyl) platinum (tricyclohexylphosphine) chloride,

(allyl) platinum (tricyclohexylphosphine) trifluoromethanesulfonate,

(1, 1-dimethylallyl) palladium (triisopropylphosphine) trifluoroacetate,

(2-chloroallyl) palladium (triisopropylphosphine) trifluoroacetate,

(crotyl) palladium (triisopropylphosphine) trifluoromethanesulfonate,

(crotyl) palladium (tricyclohexylphosphine) bistrifluoromethanesulfonylimide,

(crotyl) palladium (tricyclopentylphosphine) trifluoromethanesulfonate,

(methallyl) palladium (tricyclohexylphosphine) bistrifluoromethanesulfonylimide,

(methallyl) palladium (triisopropylphosphine) trifluoromethanesulfonate,

(methallyl) palladium (tricyclopentylphosphine) trifluoromethanesulfonate,

(methallyl) palladium (tricyclohexylphosphine) chloride,

(methallyl) palladium (triisopropylphosphine) chloride,

(methallyl) palladium (tricyclopentylphosphine) chloride,

(methallyl) palladium (tricyclohexylphosphine) bistrifluoromethanesulfonylimide,

(methallyl) palladium (triisopropylphosphine) bistrifluoromethanesulfonylimide,

(methallyl) palladium (tricyclopentylphosphine) bistrifluoromethanesulfonylimide,

(methallyl) palladium (tricyclohexylphosphine) trifluoroacetate,

(methallyl) palladium (triisopropylphosphine) trifluoroacetate,

(methallyl) palladium (tricyclopentylphosphine) trifluoroacetate,

(methallyl) palladium (tricyclohexylphosphine) acetate,

(methallyl) palladium (triisopropylphosphine) acetate,

(methallyl) palladium (tricyclopentylphosphine) acetate,

(methallyl) nickel (tricyclohexylphosphine) trifluoromethanesulfonate,

{2- [ (dimethylamino) methyl ] phenyl-C, N- } -palladium (tricyclohexylphosphine) chloride,

{ [ (dimethylamino) methyl ] phenyl-C, N- } -palladium (tricyclohexylphosphine) trifluoromethanesulfonate,

(hydrogenated) palladium bis (tricyclohexylphosphine) trifluoromethanesulfonate,

(hydrogenated) palladium bis (tricyclohexylphosphine) formate,

(hydrogenated) palladium bis (tricyclohexylphosphine) chloride,

(hydrogenated) palladium bis (triisopropylphosphine) chloride,

(hydrogenated) palladium bis (tricyclohexylphosphine) nitrate,

(hydrogenated) palladium bis (tricyclohexylphosphine) trifluoroacetate salt, and

(hydrogenated) palladium bis (triisopropylphosphine) trifluoromethanesulfonate.

Other suitable procatalyst components for use in the foregoing process include (Me)₂NCH₂C₆H₄)Pd(O₃SCF₃) P (cyclohexyl)₃(i.e., ortho-metalated phenylmethylenedimethylaminopalladium tricyclohexylphosphine),

(allyl) Pd (P-i-Pr)₃)C₆F₅(allyl) Pd (PCy)₃)C₆F₅，(CH₃)Pd(PMe₃)₂Cl，(C₂H₅)Pd(PMe₃)₂Cl(Ph)Pd(PMe₃)₂Cl，(CH₃)Pd(PMe₃)₂Br，(CH₃)Pd(PMe₂Ph)₂Cl，(C₂H₅)Pd(PMe₃)₂Br，(C₂H₅)Pd(PMe₃)₂Br，(Ph)Pd(PMe₃)₂Br，(CH₃)Pd(PMe₃)NO₃，(CH₃)Pd(P(i-Pr)₃)₂O₃SCCF₃，(η¹-benzyl) Pd (PEt)₃)₂Cl, (allyl) Pd (PMe)₃)OC(O)CH₂CH＝CH₂(allyl) Pd (AsPh)₃) Cl, (allyl) Pd (PPh)₃) Cl, (allyl) Pd (Sbph)₃) Cl, (methallyl) Pd (PPh)₃) Cl, (methallyl) Pd (AsPh)₃) Cl, (methallyl) Pd (Sbph)₃) Cl, (methallyl) Pd (PBu)₃) Cl, and (methallyl) Pd (P [ (OCH)₂)₃]CH)Cl.

In another embodiment, the catalyst may be prepared by protonating the formula in the presence of a Bronsted acid based on a WCA salt

Or by using an equivalent reaction based on the carbenium or silylium ions of the WCA salt to produce the active catalyst shown in equation 4.

In this embodiment, R' is a compound having the formula- (C)_dH_2d) A divalent hydrocarbon-based ligand of (a) forming a metallocycle together with the group 10 metal center M, wherein d' represents the number of carbon atoms in the divalent hydrocarbon-based main chain and is an integer of 3 to 10. Any hydrogen atom in the divalent hydrocarbon backbone may be linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, C₅～C₁₀Cycloalkyl and C₆～C₁₀Aryl substituted. The cycloalkyl and aryl moieties may be optionally substituted with a halogen substituent selected from the group consisting of bromo, chloro, fluoro and iodo. In another embodiment, the halogen is fluorine. In addition, any two or three alkyl substituents, together with the carbon atoms of the main chain of the hydrocarbon group to which they are attached, may form an aliphatic or aromatic ring system. The rings may be monocyclic, polycyclic or fused. Protonation occurs at one of the hydrocarbyl/metal center bonding interfaces to produce a cationic complex having a monovalent hydrocarbyl ligand coordinated to the metal center M.

In another embodiment, the group 10 metal-coordinated procatalyst has the formula [ R 'M (L')_x(L”)_yA’]Containing a group 15 electron donor ligand (L') and a labile neutral electron donor ligand (L "), is mixed in a suitable solvent with a salt of a suitable weakly coordinating anion to form a one-component catalyst product as shown in equation (5) below.

5.

Suitable compounds have the formula [ R 'M (L')_x(L”)_yA’]The procatalyst of (a) includes, but is not limited to, the following compositions:

[ (allyl) Pd (NCCH)₃)(P-i-Pr₃)][B(O₂-3，4，5，6-Cl₄C₆)₂][ (allyl) Pd (HOCH)₃)(P-i-Pr₃)][B(O₂-3，4，5，6-Cl₄C₆)₂][ (allyl) Pd (HOCH)₃)(P-i-Pr₃)][B(O₂-3，4，5，6-Br₄C₆)₂][ (allyl) Pd (HOCH)₃)(P-i-Pr₃)][B(O₂C₆H₄)₂][ (allyl) Pd (OEt)₂)(P-i-Pr₃)][BPh₄][ (allyl) Pd (OEt)₂)(P-i-Pr₃)]，[SbF₆][ (allyl) Pd (OEt)₂)(P-i-Pr₃)][BF₄][ (allyl) Pd (OEt)₂)(PCy₃)][BF₄][ (allyl) Pd (OEt)₂)(PPh₃)][BF₄][ (allyl) Pd (OEt)₂)(P-i-Pr₃)][PF₆][ (allyl) Pd (OEt)₂)(PCy₃)][PF₆][ (allyl) Pd (OEt)₂)(PPh₃)][PF₆][ (allyl) Pd (OEt)₂)(P-i-Pr₃)][ClO₄][ (allyl) Pd (OEt)₂)(PCy₃)][ClO₄][ (allyl) Pd (OEt)₂)(PPh₃)][ClO₄][ (allyl) Pd (OEt)₂)(P-i-Pr₃)][SbF₆][ (allyl) Pd (OEt)₂)(PCy₃)][SbF₆]And [ (allyl) Pd (OEt)₂)(PPh₃)][SbF₆].

In another embodiment of the invention the catalyst of formula I is formed by a process wherein the formula is [ M (L')_x(L”)_y(A’)₂]The procatalyst of (a) is reacted with an organometallic compound of aluminum, lithium, magnesium and a source of Weakly Coordinating Anions (WCA) or a strong Lewis acid. In this embodiment, the anionic hydrocarbyl ligand (R') on the group 10 metal center (M) is provided by reaction with an organometallic compound to produce the active catalyst shown below.

6.

Examples of procatalysts suitable for use in this embodiment include;

nickel (II) acetylacetonate,

the nickel (II) carboxylate is a nickel (II) carboxylate,

a nickel (II) chloride, a nickel (II),

a nickel (II) bromide, a nickel (II),

the nickel ethyl hexanoate is added into the solution,

nickel (II) trifluoroacetate, a nickel (II) trifluoroacetate,

nickel (II) hexafluoroacetylacetonate,

NiCl₂(PPh₃)₂，

NiBr₂(P (P-tolyl)₃)₂，

trans-PdCl₂(PPh₃)₂，

Palladium (II) bis (trifluoroacetic acid) salt,

the palladium (II) acetylacetonate,

(cyclooctadiene) palladium (II) dichloride,

pd (acetate)₂(PPh₃)₂，

PdCl₂(PPh₃)₂，

PdBr₂(PPh₃)₂，

PdBr₂(P (P-tolyl)₃)₂，

PdCl₂(P (o-tolyl)₃)₂，

PdCl₂(P (cyclohexyl)₃)₂，

(II) a palladium (II) bromide,

(II) a palladium (II) chloride,

a palladium (II) iodide which is a metal,

palladium (II) ethyl hexanone (II),

dichloro bis (acetonitrile) palladium (II),

dichloro bis (benzonitrile) palladium (II),

(II) a platinum (II) chloride,

platinum (II) bromide, and

platinum bis (triphenylphosphine) dichloride.

Typically, the group 10 metal procatalyst is a nickel (II), platinum (II) or palladium (II) compound containing two anionic leaving groups (A'), which can be readily displaced by either the weakly coordinating anion provided by the WCA salt or the strong Lewis acid described below, and can be displaced by a hydrocarbyl group derived from the organometallic compound. The leaving groups may be the same or different. The group 10 metal procatalyst may or may not be ligated.

When the procatalyst in this embodiment is not coordinated with the group 15 electron donor component (L'), a group 15 electron donor ligand may be added to the reaction medium, as shown in the reaction scheme below.

7.

Strong lewis acids suitable for use in this embodiment are selected from compounds having the following formula:

M’(R^41’)₃

wherein M' represents aluminum or boron and R^41’Represents mono-and polysubstituted C₆～C₃₀Aryl, wherein the substituents on the aryl are independently selected from halogen (in certain embodiments, halogen is fluorine), linear or branchedChain C₁～C₅Haloalkyl (in certain embodiments, trifluoromethyl) and halo-and perhalophenyl (in certain embodiments, pentafluorophenyl). Examples of such strong lewis acids include: tris (pentafluorophenyl) boron, tris (3, 5-bis (trifluoromethyl) phenyl) boron, tris (2, 2', 2 "-nonafluorobiphenyl) borane, and tris (pentafluorophenyl) aluminum.

The organometallic compound is a hydrocarbyl derivative of silicon, germanium, tin, lithium, magnesium or aluminum. In certain embodiments, an aluminum derivative is used. The organoaluminum component of the catalyst system is represented by the following formula:

AlR’_3-x”Q_x”

wherein R' independently represents hydrogen, linear or branched C₁～C₂₀Alkyl radical, C₅～C₁₀Cycloalkyl, linear or branched C₂～C₂₀Alkenyl radical, C₆～C₁₅Cycloalkenyl, allyl ligands or canonical forms thereof,C₆～C₂₀aryl and C₇～C₃₀Aralkyl, Q is a halide or pseudohalide selected from chlorine, fluorine, bromine, iodine, linear and unbranched C₁～C₂₀Alkoxy radical, C₆～C₂₄An aryloxy group; x' is 0 to 2.5. In another embodiment, x' is 0 to 2. In yet another embodiment, x "is 0 to 1. In certain embodiments, trialkylaluminum compounds are used. Examples of suitable organometallic compounds include: methyllithium, sec-butyllithium, n-butyllithium, phenyllithium, butylethylmagnesium, di-n-butylmagnesium, butyloctylmagnesium, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum (i-butylphenoxy) and diethylaluminum (2, 4-di-tert-butylphenoxy).

Embodiments of the catalyst lacking a hydrocarbyl ligand may be represented by the formula [ M (A')₂]The procatalyst of (a) is synthesized by reaction with the desired ligand and WCA salt according to the following reaction scheme:

8.

wherein x is 1 or 2, and M and L' are as defined above.

Examples of procatalyst compounds include palladium (II) bis (acetylacetone), palladium (acetic acid)₂、Pd(NO₃)₂、PdCl₂、PdBr₂And PdI₂。

The foregoing schematic equations (1-8) have been presented for illustrative purposes only. Although they are given in equilibrium, it should be noted that excess amounts of the reaction components may be used without departing from the spirit of the present invention. For example, components containing an excess of L ', L ", A' or WCA salt may be used in the process of the present invention, provided that the reaction process is not adversely affected.

In one embodiment, the molar ratio of group 10 metal/group 15 electron donor compound/source of weakly coordinating anion/organometallic compound is 1: 1 to 10: 1 to 100: 2 to 200. In another embodiment, the molar ratio of group 10 metal/group 15 electron donor compound/source of weakly coordinating anion/organometallic compound is 1: 1 to 5: 1 to 40: 4 to 100. In yet another embodiment, the molar ratio of group 10 metal/group 15 electron donor compound/source of weakly coordinating anion/organometallic compound is 1: 1 to 2: 2 to 20: 5 to 50. In certain embodiments, where the group 10 metal ion source is an adduct containing a group 15 electron donor compound, the use of an additional group 15 electron donor compound is not required. In this embodiment, the molar ratio of group 10 metal/group 15 electron donor compound/source of weakly coordinating anion/organometallic compound is 1: 0: 2 to 20: 5 to 50.

In all of the foregoing embodiments, the catalyst of formula I may be prepared as a preformed single component catalyst in a solvent or may be prepared in situ by mixing the precursor components (the leaving group bearing coordinating or non-coordinating group 10 metal component, the ligand component, and the WCA source or strong Lewis acid source) in the desired monomer, monomer mixture, or solution thereof. It is also possible to mix two or even three catalyst precursor components and then add the mixture to the monomer or monomer solution containing the remaining catalyst precursor components.

In the equations and formulae shown above and throughout the specification, R ', M, L ', L ", [ WCA ], b, d, x and y are as defined above, unless otherwise defined, A ' is an anionic leaving group as defined below, the [ WCA ] salt is a metal salt of a weakly coordinating anion [ WCA ], and the abbreviations Me, Et, Pr, Bu, Cy and Ph are used herein and throughout the specification to refer to methyl, ethyl, propyl, butyl, cyclohexyl and phenyl, respectively.

The aforementioned group 10 metal procatalyst components are commercially available or may be synthesized using techniques well known in the art.

As discussed above, the catalyst complex of formula I may be prepared in situ by combining any of the group 10 metal procatalysts in the monomer with the desired catalyst system components. In the case where the group 10 metal procatalyst already contains the desired ligand group, the procatalyst is mixed in the monomer with either a WCA salt or an optional activator such as a strong Lewis or Bronsted acid. A WCA salt, a strong Lewis acid or Bronsted acid in combination may act as an activator for the procatalyst when the monomers are present. The in situ reaction to prepare the catalysts of formula I generally employs the same general conditions and reaction scheme as the preparation of a preformed single component catalyst, the main difference being that the catalyst is prepared in monomer instead of in solvent and the polymeric product is formed.

Leaving group

A' represents an anionic leaving group susceptible to substitution by a weakly coordinating anion provided by the WCA salt. The leaving group forms a salt with the cation in the WCA salt. The leaving group A' is selected from the group consisting of halogen (i.e., Br, Cl, I and F), nitrate, trifluoromethanesulfonate, bistrifluoromethanesulfonylimide, trifluoroacetate, tosylate, AlBr₄ ^-、AlF₄ ^-、AlCl₄ ^-、AlF₃O₃SCF₃ ^-、AsCl₆ ^-、SbCl₆ ^-、SbF₆ ^-、PF₆ ^-、BF₄ ^-、ClO₄ ^-、HSO₄ ^-Carboxylates, acetates, acetylacetonates, carbonates, aluminates and borates.

In another embodiment, when a bronsted acid based on a WCA salt is used as activator, the leaving group may be a hydrocarbyl or a halogenated hydrocarbyl. In this embodiment, the activator protonates the hydrocarbyl or halogenated hydrocarbyl group to form a neutral moiety. In certain embodiments, the leaving group moiety is selected from hydride, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, C₅～C₁₀Cycloalkyl and C₆～C₁₀And (4) an aryl group. The cycloalkyl and aryl moieties may be optionally substituted with a halogen substituent selected from the group consisting of bromo, chloro, fluoro and iodo. In certain embodiments, the halogen is fluorine. In this embodiment, a 'is protonated to form the neutral moiety a' H. Methyl and pentaFluorophenyl is a representative example of a leaving group in this embodiment.

Halogen leaving groups include chloro, iodo, bromo and fluoro. The acetate salt comprises the formula R^38’C(O)O^-And the carbonate comprises the group of the formula R^38’OC(O)O^-Wherein R is^38’Represents linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl (in one embodiment, haloalkyl contains only fluorine), linear or branched C₁～C₅Alkenyl and C₆～C₁₂Aryl radicals, optionally substituted by linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl and halogen (in certain embodiments, fluorine) are mono-substituted or, independently, poly-substituted.

The aluminate and borate leaving groups may be of the formula M' (R)^39’)₄ ^-、M’(GR^39’)₄ ^-And M' (-C ≡ CPh)₄ ^-Represents, or is a moiety represented by the following structure:

wherein G is a sulfur or oxygen atom, Ph represents a phenyl group and a substituted phenyl group as defined below, and R^39’Independently represents a linear or branched C₁～C₁₀Alkyl, linear or branched C₁～C₁₀Chloro-or bromoalkyl, C₅～C₁₀Cycloalkyl, substituted and unsubstituted aryl (in certain embodiments, phenyl and substituted phenyl), substituted and unsubstituted C₇～C₂₀Aralkyl (in certain embodiments, phenylalkyl and substituted phenylalkyl). Substituted means that the aryl or phenyl group may contain one or several linear or branched C₁～C₅Alkane (I) and its preparation methodRadical, linear or branched C₁～C₅Haloalkyl, chloro, and bromo substituents, and combinations thereof.

Representative aluminate groups include, but are not limited to, tetraphenoxy aluminate, tetra (cyclohexyloxy) aluminate, tetraethoxy aluminate, tetramethoxy aluminate, tetra (isopropoxy) aluminate, tetra (2-butoxide) aluminate, tetrapentyloxy aluminate, tetra (2-methyl-2-propoxide) aluminate, tetra (nonoxy) aluminate, and bis (2-methoxyethanol-O, O ') bis (2-methoxyethanol-O') aluminate, tetra (phenyl) aluminate, tetra (p-tolyl) aluminate, tetra (m-tolyl) aluminate, tetra (2, 4-dimethylphenyl) aluminate, and tetra (3, 5-dimethylphenyl) aluminate.

Representative borate groups include tetraphenylborate, tetrakis (4-methylphenyl) borate, tetrakis (4-chlorophenyl) borate, tetrakis (4-bromophenyl) borate, tetrakis (2-bromo-4-chlorophenyl) borate, butyltriphenylborate, tetrakis (4-methoxyphenyl) borate, tetrakis (phenylethynyl) borate, bis (1, 2-benzenediolate) borate, triphenyl (phenylethynyl) borate, bis (tetrafluorobenzenediolate) borate, bis (tetrachlorobenzenediolate) borate, bis (tetrabromobenzenediolate) borate, bis (1, 1 '-diphenyl-2, 2' -bipholate) borate, tetrakis (thiophenolate) borate, bis (3, 5-di-tert-butylbenzoolate) borate, tetrakis (2, 4-dimethylphenyl) borate, tetrakis (4-dimethylphenyl) borate, and mixtures thereof, Tetra (p-tolyl) borate, tetra (3, 5-dimethylphenyl) borate, and tetra (m-tolyl) borate.

In addition to the anionic leaving groups described above, A' may also be an anion selected from the group consisting of highly fluorinated and perfluorinated alkylsulfonyl and arylsulfonyl-containing anions having the formula (R)^40’SO₂)₂CH^-、(R^40’SO₂)₃C^-And (R)^40’SO₂)₂N^-Wherein R is^40’Independently represents a linear or branched C₁～C₂₀Highly fluorinated and perfluorinated alkyl, C₅～C₁₅Highly fluorinated and perfluorinated cycloalkyl and C₆～C₂₂And (4) an aryl group. Optionally, the aryl and cycloalkyl groups may each contain heteroatoms in the chain of the cyclic structure. In certain embodiments, heteroatoms include divalent (non-peroxidized) oxygen (i.e., -O-), trivalent nitrogen, and hexavalent sulfur. Any two R^40’May together form a ring. When R is^40’Is cycloalkyl substitutedRadical, a heterocycloalkyl substituent or with another R^40’When taken together to form a ring, in one embodiment the ring structure contains 5 to 6 atoms, of which 1 to 2 may be heteroatoms.

In the above formula, the term highly fluorinated means that at least 50% of the carbon-bonded hydrogen atoms in the alkyl, cycloalkyl and aryl moieties are replaced by fluorine atoms. In certain embodiments, the alkyl, cycloalkyl and aryl moieties R^40’At least 2 of every 3 hydrogen atoms of (a) are substituted by fluorine. In another embodiment, at least 3 out of every 4 hydrogen atoms are substituted with fluorine. In yet another embodiment, R^40’All hydrogen atoms on the substituent are substituted with fluorine to give a perfluorinated moiety. The aryl radicals, in addition to or instead of being substituted by fluorine atoms in the aromatic ring, may contain linear or branched C₁～C₁₀Highly fluorinated and perfluorinated alkyl groups, such as trifluoromethyl. In some embodiments, the hydrogen atom remains in the alkyl group,Some or all of the remaining hydrogen atoms on the cycloalkyl and aryl moieties may be substituted with bromine and/or chlorine atoms.

Representative highly fluorinated and perfluorinated alkylsulfonyl and arylsulfonyl-containing anions of the foregoing formula include, but are not limited to

(C₂F₅SO₂)₂N^-，(C₄F₉SO₂)₂N^-，(CF₃SO₂)₂N^-，(CF₃SO₂)(C₄F₉SO₂)N^-，((CF₃)₂NC₂F₄SO₂)₂N^-，(C₆F₅SO₂)(CF₃SO₂)N^-，(CF₃SO₂)(CHF₂SO₂)N^-，(C₂F₅SO₂)(CF₃SO₂)N^-，(C₃F₇SO₂)₂N^-，((CF₃)₂(F)CSO₂)₂N^-，(C₄F₈(CF₃)₂NSO₂)₂N^-(C₈F₁₇SO₂)₃C^-，(CF₃SO₂)₃C^-，(CF₃SO₂)₂CH^-，(C₄F₉SO₂)₃C^-，(CF₃SO₂)₂(C₄F₉SO₂)C^-，((CF₃)₂NC₂F₄SO₂)C(SO₂CF₃)₂ ^-(3, 5-bis (CF)₃)C₆H₃)SO₂N(SO₂CF₃)^-，(C₆F₅SO₂)C(SO₂CF₃)₂ ^-，

An example of the structure is as follows:

the remaining highly fluorinated and perfluoroalkylsulfonyl and arylsulfonyl anions suitable as leaving groups are described in Turowsky and Seppelt, organic Chemistry, 1988, 27, 2135-; 4,505,997, respectively; 5,021,308, respectively; 5,072,040, respectively; 5,162,177 and 5,273,840, the disclosures of which are incorporated herein by reference.

WCA salt

Salts of weakly coordinating anions useful in the process of the invention may be of the formula [ C (L ")_z]_b[WCA]_dWherein C represents a proton (H)⁺) An alkaline earth metal cation, a transition metal cation or a cation containing an organic group, L' and WCA are as defined above, z is an integer of 0 to 8, and b and d represent the multiples of the cation complex and the weakly coordinating counteranion complex (WCA), respectively, for balancing the charge of the entire salt complex.

The alkali metal cation comprises a group 1 metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium. In certain embodiments, the group 1 metal cation is lithium, sodium, and potassium.

The alkaline earth metal cation comprises a group 2 metal selected from beryllium, magnesium, calcium, strontium and barium. In certain embodiments, the group 2 metal cation is magnesium, calcium, strontium, and barium. The transition metal cation is selected from zinc, silver and thallium.

The organic radical cation is selected from the group consisting of ammonium, phosphonium, carbenium and silylium cations, i.e., [ NHR ]^41’ ₃]⁺、[NR^41’ ₄]⁺、[PHR^41’ ₃]、[PR^41’ ₄]、[R^41’ ₃C]⁺And [ R ]^41’ ₃Si]⁺Wherein R is^41’Independently represents a hydrocarbyl, silylhydrocarbyl or perfluorocarbyl group, each containing 1 to 24 carbon atoms (or in another embodiment 1 to 12 carbon atoms), arranged in a linear, branched or cyclic structure. A perfluorocarbon group means that all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. Representative hydrocarbyl groups include, but are not limited to, linear or branched C₁～C₂₀Alkyl radical, C₃～C₂₀Cycloalkyl, linear or branched C₂～C₂₀Alkenyl radical, C₃～C₂₀Cycloalkenyl radical, C₆～C₂₄Aryl radical, C₇～C₂₄Aralkyl and organometallic cations. The organic cation is selected from the group consisting of trityl, trimethylsilyl cation, triethylsilyl cation, tris (trimethylsilyl) silyl cation, tritylsilyl cation, triphenylsilyl cation, tricyclohexylsilyl cation, dimethyloctadecylsilyl cation, and triphenylcarbenium ion (i.e., trityl). Ferrocenium cations such as [ (C) in addition to the above cation complexes₅H₅)₂Fe]⁺And [ (C)₅(CH₃))₂Fe]⁺May also be used as cations in the WCA salt of the present invention.

Examples of WCA salts having weakly coordinating anions described by formula II include, but are not limited to:

lithium tetrakis (2-fluorophenyl) borate,

sodium tetrakis (2-fluorophenyl) borate,

silver tetrakis (2-fluorophenyl) borate,

thallium tetrakis (2-fluorophenyl) borate,

lithium tetrakis (3-fluorophenyl) borate,

sodium tetrakis (3-fluorophenyl) borate,

silver tetrakis (3-fluorophenyl) borate,

thallium tetrakis (3-fluorophenyl) borate,

ferrocene tetrakis (3-fluorophenyl) borate,

ferrocene tetrakis (pentafluorophenyl) borate,

lithium tetrakis (4-fluorophenyl) borate,

sodium tetrakis (4-fluorophenyl) borate,

silver tetrakis (4-fluorophenyl) borate,

thallium tetrakis (4-fluorophenyl) borate,

lithium tetrakis (3, 5-difluorophenyl) borate,

sodium tetrakis (3, 5-difluorophenyl) borate,

thallium tetrakis (3, 5-difluorophenyl) borate,

trityl tetrakis (3, 5-difluorophenyl) borate,

2, 6-dimethylanilinium tetrakis (3, 5-difluorophenyl) borate,

lithium tetrakis (pentafluorophenyl) borate, a lithium salt of,

lithium (diethyl ether) tetrakis (pentafluorophenyl) borate,

lithium (diethyl ether)_2.5Tetrakis (pentafluorophenyl) borate (also referred to herein as LiFeABA),

lithium tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

lithium tetrakis (3, 4,5, 6-tetrafluorophenyl) borate,

lithium tetrakis (1, 2, 2-trifluorophenyl) borate,

lithium tetrakis (3, 4, 5-trifluorophenyl) borate,

lithium methyl tris (perfluorophenyl) borate,

lithium phenyl tris (perfluorophenyl) borate,

lithium tris (isopropanol) tetrakis (pentafluorophenyl) borate,

lithium tetrakis (methanolic) tetrakis (pentafluorophenyl) borate,

silver tetrakis (pentafluorophenyl) borate, a silver compound,

tris (toluene) silver tetrakis (pentafluorophenyl) borate,

tris (xylene) silver tetrakis (pentafluorophenyl) borate,

trityl tetrakis (pentafluorophenyl) borate,

trityl tetrakis (4-triisopropylsilyltetrafluorophenyl) borate,

trityl tetrakis (4-dimethyl-tert-butylsilyltetrafluorophenyl) borate,

thallium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate,

2, 6-dimethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

n, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate,

lithium (triphenylsiloxy) tris (pentafluorophenyl) borate,

sodium (triphenylsiloxy) tris (pentafluorophenyl) borate,

sodium tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

sodium tetrakis (3, 4,5, 6-tetrafluorophenyl) borate,

sodium tetrakis (1, 2, 2-trifluorophenyl) borate,

sodium tetrakis (3, 4, 5-trifluorophenyl) borate,

sodium methyl tris (perfluorophenyl) borate,

sodium phenyl tri (perfluorophenyl) borate,

thallium tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

thallium tetrakis (3, 4,5, 6-tetrafluorophenyl) borate,

thallium tetrakis (1, 2, 2-trifluorophenyl) borate,

thallium tetrakis (3, 4, 5-trifluorophenyl) borate,

sodium methyl tris (perfluorophenyl) borate,

thallium phenyl tris (perfluorophenyl) borate,

trityl tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

trityl tetrakis (3, 4,5, 6-tetrafluorophenyl) borate,

trityl tetrakis (1, 2, 2-trifluorophenyl) borate,

trityl tetrakis (3, 4, 5-trifluorophenyl) borate,

trityl tris (perfluorophenyl) borate,

tritylphenyl tris (perfluorophenyl) borate,

silver tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate,

silver (toluene) tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate,

thallium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate,

lithium (hexyl (pentafluorophenyl)) borate,

lithium triphenylsiloxy tris (pentafluorophenyl) borate,

lithium (octyloxy) tris (pentafluorophenyl) borate,

lithium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

sodium tetrakis (pentafluorophenyl) borate,

trityl tetrakis (pentafluorophenyl) borate,

sodium (octyloxy) tris (pentafluorophenyl) borate,

sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

potassium tetrakis (pentafluorophenyl) borate, a salt of,

trityl tetrakis (pentafluorophenyl) borate,

potassium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

magnesium tetrakis (pentafluorophenyl) borate, a crystalline form of magnesium,

magnesium (octyloxy) tris (pentafluorophenyl) borate,

magnesium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

calcium tetrakis (pentafluorophenyl) borate, a salt of,

calcium (octyloxy) tris (pentafluorophenyl) borate,

calcium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

lithium tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] phenyl ] borate,

sodium tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] phenyl ] borate,

silver tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] phenyl ] borate,

thallium tetrakis [3, 5-bis [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] phenyl ] borate,

lithium tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate,

sodium tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate,

silver tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate,

thallium tetrakis [3- [ 1-methoxy-2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate,

lithium tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate.

Sodium tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate.

Silver tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate.

Thallium tetrakis [3- [2, 2, 2-trifluoro-1- (2, 2, 2-trifluoroethoxy) -1- (trifluoromethyl) ethyl ] -5- (trifluoromethyl) phenyl ] borate.

Trimethylsilyl cation tetrakis (pentafluorophenyl) borate,

trimethylsilyl cation diethyl ether complex tetrakis (pentafluorophenyl) borate,

triethylsilyl-cationic tetrakis (pentafluorophenyl) borate,

triphenylsilyl cation tetrakis (pentafluorophenyl) borate,

tris (2, 4, 6-trityl) silyl cationium tetrakis (pentafluorophenyl) borate,

tribenzylsilyl cation tetrakis (pentafluorophenyl) borate,

trimethylsilyl cationomethyltris (pentafluorophenyl) borate,

triethylsilyl-cationic methyltris (pentafluorophenyl) borate,

triphenylsilyl-cationic methyltris (pentafluorophenyl) borate,

tribenzylsilyl cationicmethyl tris (pentafluorophenyl) borate,

trimethylsilyl cation tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

triethylsilyl-cationic tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

triphenylsilyl-cationic tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

tribenzylsilyl cation tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

trimethylsilyl cation tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

triphenylsilyl-cationic tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

trimethylsilyl cation tetrakis (3, 4, 5-trifluorophenyl) borate,

tribenzylsilyl cation tetrakis (3, 4, 5-trifluorophenyl) aluminate,

triphenylsilyl cation tetrakis (3, 4, 5-trifluorophenyl) aluminate,

triethylsilyl-cationic tetrakis (1, 2, 2-trifluorophenyl) borate,

tricyclohexylsilyl-cationic tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate,

dimethyloctadecylsilyl cation tetrakis (pentafluorophenyl) borate,

tris ((trimethyl) silyl) silylium methyl tris (2, 3, 4, 5-tetrafluorophenyl) borate,

2,2 '-dimethyl-1, 1' -binaphthylmethylsilyl cation tetrakis (pentafluorophenyl) borate,

2,2 '-dimethyl-1, 1' -binaphthylmethylsilyl cation tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,

lithium tetrakis (pentafluorophenyl) aluminate is provided,

trityl tetrakis (pentafluorophenyl) aluminate,

a trityl (perfluorobiphenyl) fluoroaluminate,

lithium (octyloxy) tris (pentafluorophenyl) aluminate,

lithium tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate,

sodium tetrakis (pentafluorophenyl) aluminate is added to the reaction mixture,

trityl tetrakis (pentafluorophenyl) aluminate,

sodium (octyloxy) tris (pentafluorophenyl) aluminate,

sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate,

potassium tetrakis (pentafluorophenyl) aluminate is added to the mixture,

trityl tetrakis (pentafluorophenyl) aluminate,

potassium (octyloxy) tris (pentafluorophenyl) aluminate,

potassium tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate,

magnesium tetrakis (pentafluorophenyl) aluminate is used as the starting material,

magnesium (octyloxy) tris (pentafluorophenyl) aluminate,

magnesium tetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate,

calcium tetrakis (pentafluorophenyl) aluminate is added to the reaction mixture,

calcium (octyloxy) tris (pentafluorophenyl) aluminate,

caltetrakis (3, 5-bis (trifluoromethyl) phenyl) aluminate,

examples of WCA salts having weakly coordinating anions described by formula III include, but are not limited to

LiB(OC(CF₃)₃)₄，LiB(OC(CF₃)₂(CH₃))₄，LiB(OC(CF₃)₂H)₄，LiB(OC(CF₃)(CH₃)H)₄，TlB(OC(CF₃)₃)₄，TlB(OC(CF₃)₂H)₄，TlB(OC(CF₃)(CH₃)H)₄，TlB(OC(CF₃)₂(CH₃))₄，(Ph₃C)B(OC(CF₃)₃)₄，(Ph₃C)B(OC(CF₃)₂(CH₃))₄，(Ph₃C)B(OC(CF₃)₂H)₄，(Ph₃C)B(OC(CF₃)(CH₃)H)₄，AgB(OC(CF₃)₃)₄，AgB(OC(CF₃)₂H)₄，AgB(OC(CF₃)(CH₃)H)₄，LiB(O₂C₆F₄)₂，TlB(O₂C₆F₄)₂Ag (toluene)₂B(O₂C₆F₄)₂And Ph₃CB(O₂C₆F₄)₂，LiB(OCH₂(CF₃)₂)₄，[Li(HOCH₃)₄]B(O₂C₆Cl₄)₂，[Li(HOCH₃)₄]B(O₂C₆F₄)₂[ Ag (toluene)₂]B(O₂C₆Cl₄)₂，LiB(O₂C₆Cl₄)₂，(LiAl(OC(CF₃)₂Ph)₄)，(TlAl(OC(CF₃)₂Ph)₄)，(AgAl(OC(CF₃)₂Ph)₄)，(Ph₃CAl(OC(CF₃)₂Ph)₄，(LiAl(OC(CF₃)₂C₆H₄CH₃)₄)，(ThAl(OC(CF₃)₂C₆H₄CH₃)₄)，(AgAl(OC(CF₃)₂C₆H₄CH₃)₄)，(Ph₃CAl(OC(CF₃)₂C₆H₄CH₃)₄)，LiAl(OC(CF₃)₃)₄，ThAl(OC(CF₃)₃)₄，AgAl(OC(CF₃)₃)₄，Ph₃CAl(OC(CF₃)₃)₄，LiAl(OC(CF₃)(CH₃)H)₄，TlAl(OC(CF₃)(CH₃)H)₄，AgAl(OC(CF₃)(CH₃)H)₄，Ph₃CAl(OC(CF₃)(CH₃)H)₄，LiAl(OC(CF₃)₂H)₄，TlAl(OC(CF₃)₂H)₄，AgAl(OC(CF₃)₂H)₄，Ph₃CAl(OC(CF₃)₂H)₄，LiAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄，TlAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄，AgAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄，Ph₃CAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄，LiAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄，TlAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄，AgAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄，Ph₃CAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄，LiAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄，TlAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄，AgAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄，Ph₃CAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄，LiAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄，TlAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄，AgAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄，Ph₃CAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄，LiAl(OC(CF₃)₂C₆H₂-2，6-(CF₃)₂-4-Si-i-Pr₃)₄，TlAl(OC(CF₃)₂C₆H₂-2，6-(CF₃)₂-4-Si-i-Pr₃)₄，AgAl(OC(CF₃)₂C₆H₂-2，6-(CF₃)₂-4-Si-i-Pr₃)₄，Ph₃CAl(OC(CF₃)₂C₆H₂-2，6-(CF₃)₂-4-Si-i-Pr₃)₄，LiAl(OC(CF₃)₂C₆H₃-3，5-(CF₃)₂)₄，TlAl(OC(CF₃)₂C₆H₃-3，5-(CF₃)₂)₄，AgAl(OC(CF₃)₂C₆H₃-3，5-(CF₃)₂)₄，Ph₃CAl(OC(CF₃)₂C₆H₃-3，5-(CF₃)₂)₄，LiAl(OC(CF₃)₂C₆H₂-2，4，6-(CF₃)₃)₄，TlAl(OC(CF₃)₂C₆H₂-2，4，6-(CF₃)₃)₄，AgAl(OC(CF₃)₂C₆H₂-2，4，6-(CF₃)₃)₄，Ph₃CAl(OC(CF₃)₂C₆H₂-2，4，6-(CF₃)₃)₄，LiAl(OC(CF₃)₂C₆F₅)₄，TlAl(OC(CF₃)₂C₆F₅)₄，AgAl(OC(CF₃)₂C₆F₅)₄And Ph₃CAl(OC(CF₃)₂C₆F₅)₄.

Examples of boratabenzene salts include, but are not limited to: [1, 4-dihydro-4-methyl-1- (pentafluorophenyl) ] -2-boralkyllithium, [1, 4-dihydro-4-methyl-1- (pentafluorophenyl) ] -2-boraalkyltriphenylmethyl cation, 4- (1, 1-dimethyl) -1, 2-dihydro-1- (pentafluorophenyl) -2-boralkyllithium, 4- (1, 1-dimethyl) -1, 2-dihydro-1- (pentafluorophenyl) -2-boraalkyltriphenylmethyl cation, 1-fluoro-1, 2-dihydro-4- (pentafluorophenyl) -2-boralkyllithium, 1-fluoro-1, 2-dihydro-4- (pentafluorophenyl) -2-boraalkyltriphenylmethyl cation The positive ions, 1- [3, 5-bis (trifluoromethyl) phenyl ] -1, 2-dihydro-4- (pentafluorophenyl) -2-boralkyllithium, and 1- [3, 5-bis (trifluoromethyl) phenyl ] -1, 2-dihydro-4- (pentafluorophenyl) -2-boraalkyltriphenylmethyl positive ion.

WCA carborane and halocarborane salts include but are not limited to silver dodecahydro-1-carbadodecaborate,

LiCB₁₁(CH₃)₁₂，LiCB₁₁H₁₂，(Me₃NH)[CB₁₁H₁₂]，(Me₄N)[1-C₂H₅CB₁₁H₁₁]，(Me₄N)[1-Ph₃SiCB₁₁H₁₁]，(Me₄N)[1-CF₃CB₁₁H₁₁]，Cs[12-BrCB₁₁H₁₁]，Ag[12-BrCB₁₁H₁₁]，Cs[7，12-Br₂CB₁₁H₁₀]，Cs[12-ClCB₁₁H₁₁]，Cs[7，12-Cl₂CB₁₁H₁₀]，Cs[1-H-CB₁₁F₁₁]，Cs[1-CH₃-CB₁₁F₁₁]，(i-Pr₃)Si[1-CF₃-CB₁₁F₁₁]，Li[12-CB₁₁H₁₁F]，Li[7，12-CB₁₁H₁₁F₂]，Li[7，9，12-CB₁₁H₁₁F₃]，(i-Pr₃)Si[CB₁₁H₆Br₆]，Cs[CB₁₁H₆Br₆]，Li[6-CB₉H₉F]，Li[6，8-CB₉H₈F₂]，Li[6，7，8-CB₉H₇F₃]，Li[6，7，8，9-CB₉H₆F₄]，Li[2，6，7，8，9-CB₉H₅F₅]，Li[CB₉H₅Br₅]，Ag[CB₁₁H₆Cl₆]，Tl[CB₁₁H₆Cl₆]，Ag[CB₁₁H₆F₆]，Tl[CB₁₁H₆F₆]，Ag[CB₁₁H₆I₆]，Tl[CB₁₁H₆I₆]，Ag[CB₁₁H₆Br₆]，Tl[CB₁₁H₆Br₆]，Li[6，7，9，10，11，12-CB₁₁H₆F₆]，Li[2，6，7，8，9，10-CB₉H₅F₅]，Li[1-H-CB₉F₉]，Tl[12-CB₁₁H₁₁(C₆H₅)]，Ag[1-C₆F₅-CB₁₁H₅Br₆]，Li[CB₁₁Me₁₂]，Li[CB₁₁(CF₃)₁₂]，Li[CB₁₁H₆I₆]，Li[CB₉H₅Br₅]，Li[Co(B₉C₂H₁₁)₂]，Li[CB₁₁(CH₃)₁₂]，Li[CB₁₁(C₄H₉)₁₂]，Li[CB₁₁(C₆H₁₃)₁₂]，Na[Co(C₂B₉H₁₁)₂]and Na [ Co (Br) ]₃C₂B₉H₈)₂].

Wherein Me represents a "methyl group". Other halocarborane salts are disclosed in International patent publication No. WO98/43983, which is incorporated herein by reference.

Monomer

The catalysts of the invention are suitable for the preparation of a wide range of polymers containing cyclic repeating units. The cyclic polymers are prepared by addition polymerization of polycycloolefin monomers in the presence of catalytic amounts of a catalyst of formula I or in the presence of the procatalyst components described above. The monomers may be polymerized by solution polymerization or bulk polymerization techniques. As defined herein, the terms "polycycloolefin," "polycyclic," and "norbornene-type" monomers are used interchangeably and mean that the monomers contain at least one norbornene moiety as shown below:

wherein X' represents oxygen, nitrogen with hydrogen or a linear or branched chain C bonded thereto₁～C₁₀Alkyl, sulfur or formula- (CH)₂)_n’-wherein n' is an integer of 1 to 5.

The simplest polycyclic monomer of the present invention is the bicyclic monomer, bicyclo [2.2.1] hept-2-ene, commonly referred to as norbornene. The term norbornene-type monomer is meant to include norbornene, substituted norbornenes and optionally substituted and unsubstituted higher cyclic derivatives thereof, as long as the monomer contains at least one moiety of norbornene-type or substituted norbornene-type. In certain embodiments, the substituted norbornene-type monomers and higher derivatives thereof contain pendant hydrocarbyl substituents or pendant functional substituents having oxygen atoms. In one embodiment, the norbornene-type or polycycloolefin monomer is represented by the following structure:

wherein each X' is independently defined as above, "a" represents a single or double bond, R¹～R⁴Independently represents hydrogen, a hydrocarbyl group or a functional substituent, m is an integer of 0 to 5, and when "a" is a double bond, R is¹、R²One and R³、R⁴One of which is not present.

When the substituent is a hydrocarbyl group, R¹～R⁴Can be a halogenated hydrocarbon group or a perhalogenated hydrocarbon group, or even a perhalogenated carbyl group (e.g., trifluoromethyl). In a certain embodiment, R¹～R⁴Independently of each otherRepresents a hydrocarbon radical, a halogenated hydrocarbon radical and a perhalogenated hydrocarbon radical selected from hydrogen, linear or branched C₁～C₁₀Alkyl, linear or branched C₂～C₁₀Alkenyl, linear or branched C₂～C₁₀Alkynyl, C₄～C₁₂Cycloalkyl radical, C₄～C₁₂Cycloalkenyl radical, C₆～C₁₂Aryl and C₇～C₂₄Aralkyl radical, R¹And R²Or R³And R⁴May together represent C₁～C₁₀An alkylidene group. Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Representative alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and cyclohexenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative aryl groups include, but are not limited to, phenyl, naphthyl, and anthracenyl. Representative aralkyl groups include, but are not limited to, benzyl and phenethyl. Representative alkylidene groups include methylidene and ethylidene.

In certain embodiments, perhalogenated hydrocarbon groups include perhalogenated phenyl and alkyl groups. Haloalkyl groups useful in the present invention are partially or fully halogenated, and are linear or branched, and have the formula C_zX”_2z+1Wherein X "is independently halogen or hydrogen as set forth above, and z is selected from an integer of 1 to 20. In another embodiment, each X "is independently selected from hydrogen, chlorine, fluorine and/or bromine. In yet another embodiment, each X "is independently hydrogen or fluorine.

In certain embodiments, the perfluorinated substituents include perfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, and perfluorohexyl. In addition to halogen substituents, the cycloalkyl, aryl and aralkyl groups of the present invention may be further substituted with linear or branched C₁～C₅Alkyl and haloalkyl, aryl and cycloalkyl.

When the pendant group is a functional substituent, R¹～R⁴Independently represent a group selected from

(CH₂)_n-CH(CF₃)₂-O-Si(Me)₃，-(CH₂)_n-CH(CF₃)₂-O-CH₂-O-CH₃，-(CH₂)_n-CH(CF₃)₂-O-C(O)-O-C(CH₃)₃，-(CH₂)_n-C(CF₃)₂-OH，-(CH₂)_nC(O)NH₂，-(CH₂)_nC(O)Cl，-(CH₂)_nC(O)OR⁵，-(CH₂)_n-OR⁵，-(CH₂)_n-OC(O)R⁵，-(CH₂)_n-C(O)R⁵，-(CH₂)_n-OC(O)OR⁵，-(CH₂)_nSi(R⁵)₃，-(CH₂)_nSi(OR⁵)₃，-(CH₂)_n-O-Si(R⁵)₃And- (CH)₂)_nC(O)OR⁶

Wherein n independently represents an integer of 0 to 10 and R⁵Independently represent hydrogen, linear or branched C₁～C₂₀Alkyl, linear or branched halogenated or perhalogenated C₁～C₂₀Alkyl, linear or branched C₂～C₁₀Alkenyl, linear or branched C₂～C₁₀Alkynyl, C₅～C₁₂Cycloalkyl radical, C₆～C₁₄Aryl radical, C₆～C₁₄Halogenated or perhalogenated aryl and C₇～C₂₄An aralkyl group. According to R⁵Representative of the definitions ofWith a hydrocarbon radical as defined above in accordance with R¹～R⁴The defined hydrocarbyl groups are the same. As above R¹～R⁴Proposed, is defined as R⁵The hydrocarbon group (b) may be halogenated or perhalogenated. For example, when R is⁵Is C₁～C₂₀When halogenated or perhalogenated alkyl, it is possible to use the formula C_zX”_2z+1Wherein z and X' are as defined above. And alkyl radicalsAt least one of the above X' must be halogen (e.g., Br, Cl or F). It should be recognized that when the alkyl group is perhalogenated, all X "substituents are halogenated. Examples of perhaloalkyl groups include, but are not limited to, trifluoromethyl, trichloromethyl, -C₇F₁₅and-C₁₁F₂₃. Examples of perhalogenated aryl groups include, but are not limited to, pentachlorophenyl and pentafluorophenyl. R⁶The radical represents an acid-labile moiety selected from the group consisting of-C (CH)₃)₃、-Si(CH₃)₃、-CH(R⁷)OCH₂CH₃、-CH(R⁷)OC(CH₃)₃Or the following cyclic group:

wherein R is⁷Represents hydrogen or linear or branched (C)₁～C₅) An alkyl group. Alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, tert-pentyl and neopentyl. In the above structure, the single bond line extending from the cyclic group indicates the position at which the cyclic protecting group is bonded to the acid substituent. R⁶Examples of the group include 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl, 3-oxohexanoyl, 3-methyl-3, 5-dihydroxy-pentyl-lactone, 1-ethoxyethyl and 1-tert-butoxyethyl.

R⁶The radicals may also represent dicyclopropylmethyl (Dcpm) and dimethylcyclopropylmethyl (Dmcp), which are represented by the following structures;

and

in structure VII above, R¹、R⁴And together with the two ring carbon atoms to which they are attached, may represent a substituted or unsubstituted cycloaliphatic radical containing from 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl radical containing from 6 to 18 ring carbon atoms or combinations thereof. The cycloaliphatic radical may be monocyclic or polycyclic. When unsaturated, the ring may compriseMono-or polyunsaturated. In a certain embodiment, the unsaturated cyclic group is a mono-unsaturated cyclic group. When substituted, the ring comprises mono-or polysubstitution, wherein the substituents are independently selected from hydrogen, linear or branched C₁～C₅Alkyl, linear or branched C₁～C₅Haloalkyl, linear or branched C₁～C₅Alkoxy, halogen, or combinations thereof. R¹And R⁴May together form a divalent bridging group, -C (O) -Q- (O) C-, which when taken together with the two ring carbon atoms to which they are attached forms a five-membered ring, wherein Q represents an oxygen atom or a group N (R)⁸) And R is⁸Selected from hydrogen, halogen, linear or branched C₁～C₁₀Alkyl and C₆～C₁₈And (4) an aryl group. Representative structures are shown below:

wherein each X' is independently defined above and m is an integer of 0 to 5.

Deuterium-enriched norbornene-type monomers in which at least one hydrogen atom and/or at least one pendant hydrocarbyl substituent R on the norbornene-type moiety is desirable within the scope of the present invention¹～R⁴The hydrogen atoms in (a) are replaced by deuterium atoms. In certain embodiments, at least 40% of the hydrogen atoms on the norbornene-type moiety and/or the hydrocarbon group substituent are replaced with deuterium. In another embodiment, at least 50% of the hydrogen atoms on the norbornene-type moiety and/or the hydrocarbon group substituent are replaced with deuterium. In yet another embodiment, at least 60% of the hydrogen atoms on the norbornene-type moiety and/or the hydrocarbon group substituent are replaced with deuterium. In one embodiment, the deuterated monomers are represented by the following structure:

wherein X' "is as defined above and R is^DIs deuterium, "i" is an integer of 0 to 6, with the proviso that when "i" is 0, R^1DAnd R^2DMust be present, R¹And R²Independently represents a hydrocarbyl or functional substituent as defined above,and R is^1DAnd R^2DMay or may not be present and independently represent a deuterium atom or deuterium-enriched hydrocarbon group containing at least one deuterium atom. In certain embodiments, the deuterated hydrocarbon group is selected from linear or branched C₁～C₁₀Alkyl wherein at least 40% of the hydrogen atoms of the carbon backbone are replaced by deuterium. In another embodiment, the deuterated hydrocarbon group is selected from linear or branched C₁～C₁₀Alkyl wherein at least 50% of the hydrogen atoms of the carbon backbone are replaced by deuterium. In yet another embodiment, the deuterated hydrocarbon group is selected from linear or branched C₁～C₁₀Alkyl wherein at least 60% of the hydrogen atoms of the carbon backbone are replaced by deuterium.

The crosslinked polymer can be prepared by copolymerization of the norbornene-type monomer represented by structure VII with a multifunctional norbornene-type crosslinking monomer. By multifunctional norbornene-type crosslinking monomer is meant that the crosslinking monomer contains at least two norbornene-type moieties (norbornene-type double bonds), each functional group being polymerizable in the presence of the catalyst system of the present invention. Crosslinkable monomers include fused polycyclic systems and linked polycyclic systems. Examples of fused cross-linking agents are shown in the following structures. Briefly, norbornadiene is included as a fused polycyclic crosslinker and is believed to contain two polymerizable norbornene-type double bonds.

Wherein Y represents a methylene group (-CH)₂-) and m represents an integer of 0 to 5, and when m is 0, Y represents a single bond. Representative monomers having the foregoing formula are shown below:

the bonded polycyclic crosslinker is generally shown in structure VIII below:

wherein "a" independently represents a single bond or a double bond, m independently represents an integer of 0 to 5, R⁹Is a divalent group selected from the group consisting of divalent hydrocarbon groups, divalent ether groups and divalent silyl groups, and n is equal to 0 or 1. IIValency means that the free valency at each end of the group is attached to a norbornene-type moiety. In one embodiment, the divalent hydrocarbon group is an alkylene group or a divalent aromatic group. Alkylene of the formula- (C)_dH_2d) -represents, wherein d represents the number of carbon atoms in the alkylene chain and is an integer of 1 to 10. Alkylene in one embodiment is selected from linear or branched (C)₁～C₁₀) Alkylene groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene. When a branched alkylene group is contemplated, it is understood that the hydrogen atoms on the alkylene backbone are linear or branched (C)₁～C₅) Alkyl substitution.

The divalent aromatic group is selected from divalent phenyl and divalent naphthyl. group-R for divalent Ether radical¹⁰-O-R¹⁰-represents wherein R¹⁰Independently of R⁹The same is true. Examples of specific bonded polycyclic crosslinkers are represented in structures VIIIa through VIIIc below:

in certain embodiments, the crosslinking agent is selected from the structures shown below:

it is dimethylbis [ bicyclo [2.2.1] hept-2-en-5-methoxy ] silane (also referred to herein as dimethylbis (norbornenemethoxy) silane),

wherein n is 1 to 4.

And

certain other types of norbornene-based crosslinkers include, but are not limited to, the structures represented in formulas a through m below.

In another embodiment, a fluorine-containing norbornene-based crosslinker is used. For example, in certain embodiments, one or more of the following fluoronorbornene crosslinking agents are used.

F-crosslinking agent I

And

F-Cross-linker II

Norbornadiene may be used as a crosslinking agent in the present invention. In another embodiment, higher homologues are used. Norbornadiene can be converted to higher homologues or Diels-Alder products by using various dimerization catalysts or heating with cyclopentadiene. In the case of the cross-linking monomer norbornadiene dimer, a selective synthesis was used in which norbornadiene catalytic coupling produced an isomeric mixture of norbornadiene dimers, shown below:

dimerization of norbornadiene is readily accomplished by a variety of catalysts, yielding a mixed composition of up to 6 isomers, Wu et al, U.S. patent 5,545,790. In a certain embodiment, the isomers are exo-trans-exo, endo-trans-endo, and-exo-trans-endo-1, 4, 4a, 4b, 5, 8, 8a, 8 b-octahydro-1, 4: 5, 8-Bimethanobiphenylene ('norbornadiene dimer' or '[ NBD)']₂"). In another embodiment, exo-trans-exoNorbornadiene dimer is used as a crosslinking agent. Higher oligomers of norbornadiene dimer are formed by heating norbornadiene dimer with dicyclopentadiene or cyclopentadiene. Other crosslinking agents are prepared by reacting cyclopentadiene with an olefin containing 2 or more reactive olefins, for example, cyclooctadiene, 1, 5-hexadiene, 1, 7-octadiene, and tricycloheptatriene.

In one embodiment, the crosslinkable monomers are those containing 2 reactive norbornene-type moieties (containing two polymerizable double bonds). In another embodiment, the monomer is prepared by reacting 5- (3-butenyl) bicyclo [2.2.1]5, 5' - (1, 2-ethylidene) bicyclo [2.2.1] prepared by Diels-Alder reaction of hept-2-ene and cyclopentadiene]Hept-2-ene (NBCH)₂CH₂NB). 5- (3-butenyl) bicyclo [2.2.1]The higher homologs of hept-2-ene are also the comonomers of choice, i.e., 2- (3-butenyl) -1, 2, 3, 4, 4a, 5, 8, 8a, -octahydro-1, 4: 5, 8-bis (methano) naphthalene. Likewise, 1,4, 4a, 5, 6, 6a, 7, 10, 10a, 11, 12, 12 a-dodecahydro-1, 4: 7, 10-bis (methylene) dibenzoxazole [ a, e [ ]]Cyclooctene is prepared in a Diels Alder reaction between 1,4, 4a, 5, 6, 9, 10, 10 a-octahydro-1, 4-methano-benzazolocyclooctene and cyclopentadiene. The higher homologs of 1,4, 4a, 5, 6, 9, 10, 10 a-octahydro-1, 4-methano-benzazolocyclooctene are also the comonomers of choice, i.e., 1,4, 4a, 5, 5a, 6, 7, 10, 11, 11a, 12, 12 a-dodecahydro-1, 4: 5, 12-bis (methylene) cyclooctane [ b]Naphthalene. Symmetric and asymmetric trimers of cyclopentadiene are also useful crosslinking agents, i.e., 4a, 4b, 5, 8, 8a, 9, 9 a-octahydro-1, 4: 5, 8-dimethano-1H-fluorene and 3a, 4, 4a, 5, 8, 8a, 9, 9 a-octahydro-4, 9: 5, 8-bis (methylene) -1H-benzo [ f)]Indene. In yet another embodiment, the monomer is derived from cyclopentaneDiene and norbornadiene, i.e., 1,4, 4a, 5, 8, 8 a-hexahydro-1, 4: 5, 8-bis (methano) naphthalene. Divinylbenzene and an excess of cyclopentadiene form the symmetrical crosslinker 5, 5' - (1, 4-phenylene) bicyclo [2.2.1]Hept-2-ene.

The economic route to the preparation of hydrocarbyl-substituted and functionally-substituted norbornene monomers by means of Diels-Alder addition reactions is generally represented by the following reaction scheme in which CPD or substituted CPD is reacted at elevated temperature with a suitable dienophile to form a substituted norbornene-type adduct:

wherein R is¹～R⁴Independently represent hydrogen, hydrocarbyl and/or functional groups as previously described.

Other norbornene-type adducts can be prepared by thermal pyrolysis of dicyclopentadiene (DCPD) in the presence of a suitable dienophile. This reaction proceeds by an initial pyrolysis of DCPD to CPD, followed by a Diels-Alder addition reaction of CPD with a dienophile, yielding the adduct shown below:

wherein n represents the number of ring units in the monomer, and R¹～R⁴Independently representing hydrogen, hydrocarbyl and/or functional groups as defined above, norbornadiene and its higher Diels-Alder adducts can likewise be prepared by thermal reaction of CPD and DCPD in the presence of acetylenic reactants, as shown below:

wherein n, R¹And R²As defined above.

Deuterium enriched norbornene-type monomers can be prepared by reaction at D₂O and a base such as NaOH by heating the DCPD in the presence of a base to form deuterated CPD, which in turn can be reacted with a dienophile (equation 1) or a deuterated dienophile (equation 2) to yield deuterated norbornene containing a pendant deuterated hydrocarbyl substituent or a pendant hydrocarbyl substituent, respectively. In another embodiment, the non-deuterated CPD can be reacted with a deuterium-enriched dienophile to produce norbornene containing deuterium-enriched hydrocarbon-based pendant groups (equation 3).

In equations 1 and 2 above, R¹～R⁴、R^1DAnd R^2DAs defined above. And i' is an integer of 1 to 6.

Examples of polymerizable norbornene-type monomers include, but are not limited to, norbornene (bicyclo [2.2.1] hept-2-ene),

(ii) a 5-acetal norbornene, a process for the preparation of a norbornene comprising the steps of,

the reaction mixture of dicyclopentadiene and dicyclopentadiene is mixed,

tricyclic [5.2.1.0^2，6]The content of the deca-8-ene,

5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methylbicyclo [2.2, 1] hept-2-ene-5-carboxylic acid,

5-methylbicyclo [2.2, 1] hept-2-ene,

5-ethylbicyclo [2.2, 1] hept-2-ene,

5-ethoxycarbonylbicyclo [2.2, 1] hept-2-ene,

5-n-propoxycarbonylbicyclo [2.2, 1] hept-2-ene,

5-isopropoxycarbonylbicyclo [2.2, 1] hept-2-ene,

5-n-butyloxycarbonyl-bicyclo [2.2, 1] hept-2-ene,

5- (2-methylpropoxy) carbonylbicyclo [2.2, 1] hept-2-ene,

5- (1-methylpropoxy) carbonylbicyclo [2.2, 1] hept-2-ene,

5-tert-butoxycarbonylbicyclo [2.2, 1] hept-2-ene,

5-cyclohexyloxycarbonybicyclo [2.2, 1] hept-2-ene,

5- (4' -tert-butylcyclohexyloxy) carbonylbicyclo [2.2, 1] hept-2-ene,

5-phenoxycarbonylbicyclo [2.2, 1] hept-2-ene,

5-tetrahydrofuryloxycarbonylbicyclo [2.2, 1] hept-2-ene,

5-tetrahydropyranyloxycarbonylbicyclo [2.2, 1] hept-2-ene,

bicyclo [2.2.1] hept-2-ene-5-carboxylic acid,

5-acetoxybicyclo [2.2.1] hept-2-ene,

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-isopropoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-n-butyloxycarbonyl-bicyclo [2.2.1] hept-2-ene,

5-methyl-5- (2-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5- (1-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5- (4' -tert-butylcyclohexyloxy) carbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-tetrahydrofuryloxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-acetoxybicyclo [2.2.1] hept-2-ene,

5-methyl-5-cyanobicyclo [2.2.1] hept-2-ene,

5, 6-bis (methoxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-bis (ethoxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-bis (n-propoxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-bis (isopropoxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-bis (n-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-bis (phenoxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-bis (tetrahydrofuryloxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-bis (tetrahydropyranyloxycarbonyl) bicyclo [2.2.1] hept-2-ene,

5, 6-dicarboxydibicyclo [2.2.1] hept-2-ene,

8-Methoxycarbonyltetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Ethoxycarbonyltetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-n-propoxycarbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Isopropoxycarbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-n-Butoxycarbonyl tetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8- (2-Methylpropoxy) carbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8- (1-Methylpropoxy) carbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-tert-Butoxycarbonyl-tetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Cyclohexyloxycarbonyl tetracyclo [4.4.0.1 ] -^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8- (4' -tert-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Phenoxycarbonyl tetracyclic [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Tetrahydropyranoxycarbonyl tetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-acetoxycarbonyltetracyclo [4.4.0.1 ] -^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-ethoxycarbonyltetra-ethylCyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-isopropoxycarbonyl tetracyclic [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8- (2-methylpropoxy) carbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8- (1-methylpropoxy) carbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-tert-butoxycarbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-cyclohexyloxycarbonyl tetracyclo [ 4.4.0.1%^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8- (4' -tert-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-phenoxycarbonyl tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-tetrahydrofuryloxycarbonyltetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-acetoxycarbonyltetracyclo [ 4.4.0.1%^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-cyanotetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (methoxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (ethoxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-di (n-propoxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (isopropoxycarbonyl) tetracyclic [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (n-butoxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (tert-butoxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (cyclohexyloxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (phenoxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (tetrahydrofuryloxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-bis (tetrahydropyranyloxycarbonyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

dicarboxy anhydride tetracyclic [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

tetracyclic [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

tetracyclic [4.4.0.1^2，5.1^7，10]A dodec-3-ene-8-carboxylic acid,

8-methyltetracyclo [4.4.0.1 ] -^2，5.1^7，10]A dodec-3-ene-8-carboxylic acid,

8-methyltetracyclo [4.4.0.1 ] -^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Ethyltetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Fluorotetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Fluoromethyl tetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Difluoromethyltetracyclo [ 4.4.0.1%^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Trifluoromethyltetracyclo [4.4.0.1 ] -^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-Pentafluoroethyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8-Difluorocyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-Difluorocyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8-bis (trifluoromethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9- (trifluoromethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8-trifluoromethyl tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8, 9-Trifluorotetracyclo [ 4.4.0.1%^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8, 9-Tri (trifluoromethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8, 9, 9-Tetrafluorotetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8, 9, 9-Tetrakis (trifluoromethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8-difluoro-9, 9-bis (trifluoromethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-difluoro-8, 9-bis (trifluoromethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8, 9-trifluoro-9-trifluoromethyl tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8, 9-trifluoro-9-trifluoromethoxy tetracyclo [4.4.0.1 ]^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 8, 9-trifluoro-9-pentafluoropropoxy tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-fluoro-8-pentafluoroethyl-9, 9-bis (trifluoromethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-chloro-8, 9, 9-trifluorotetracyclo [ 4.4.0.1%^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8, 9-dichloro-8, 9-bis (trifluoromethyl) tetracyclo [ 4.4.0.1%^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8- (2, 2, 2-Trifluorocarboxyethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

8-methyl-8- (2, 2, 2-trifluorocarboxyethyl) tetracyclo [4.4.0.1^2，5.1^7，10]A (3-dodecene) in a cyclic structure,

tricyclic [4.4.0.1 ]^2，5](ii) an undec-3-ene,

tricyclic [6.2.1.0 ]^1，8](ii) an undec-9-ene,

tetracyclic [4.4.0.1^2，5.1^7，10.0^1，6]A (3-dodecene) in a cyclic structure,

8-methyltetracyclo [4.4.0.1 ] -^2，5.1^7，10.0^1，6]A (3-dodecene) in a cyclic structure,

8-Acetal Tetracyclo [4.4.0.1^2，5.1^7，12]A (3-dodecene) in a cyclic structure,

8-Acetal Tetracyclo [4.4.0.1^2，5.1^7，10.0^1，6]A (3-dodecene) in a cyclic structure,

pentacyclic ring [6.5.1.1^3，6.0^2，7.0^9，13]The pentadec-4-ene is used as the main component,

pentacyclic ring [7.4.0.1^2，5.1^9，12.0^8，13]The pentadec-3-ene is a pentadec-3-ene,

5- (n-hexyl) -bicyclo [2.2.1] hept-2-ene,

5- (ethoxysilyl) -bicyclo [2.2.1] hept-2-ene, and

bicyclo [2.2.1] hept-2-en-5-methoxy-biphenylmethylsilane (also referred to herein as biphenylmethyl (norbornenemethoxy) silane).

Examples of polymerizable norbornene-type monomers include, but are not limited to, norbornene (bicyclo [2.2.1] hept-2-ene), 5-methyl-norbornene, ethylnorbornene, propylnorbornene, isopropylnorbornene, butylnorbornene, isobutylnorbornene, pentylnorbornene, hexylnorbornene, heptylnorbornene, octylnorbornene, decylnorbornene, dodecylnorbornene, octadecylnorbornene, trimethoxysilylnorbornene, butoxynorbornene, p-tolylnorbornene, methylalnorbornene, phenylnorbornene, acetal norbornene, vinylnorbornene, exo-dicyclopentadiene, endo-dicyclopentadiene, tetracyclododecene, methyltetracyclododecene, dimethyltetracyclododecene, ethyltetracyclododecene, ethyltetracy, Acetalonyltetracyclododecene, phenyltetracyclododecene, cyclopentadienetetramer, propenylnorbornene, 5, 8-methylene-5 a, 8 a-dihydrofluorene, cyclohexenylnorbornene, dioxamethylenehexahydronaphthalene, 2, 3-dimethoxynorbornadiene, 5, 6-bis (chloromethyl) bicyclo [2.2.1] hept-2-ene, 5-tris (ethoxy) silylnorbornene, 2-methylsilylbicyclo [2.2.1] hept-2, 5-diene, 2, 3-bistrifluoromethylbicyclo [2.2.1] hept-2, 5-diene, 5-fluoro-5-pentafluoroethyl-6-, 6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-difluoro-5-heptafluoroisopropyl-6-trifluoromethylbicyclo [2.2.1] hept-2- Alkene, 2, 3, 3, 4, 4,5, 5, 6-octafluorotricyclo [5.2.1.0] dec-8-ene, and 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-a-naphthyl-2-norbornene, 5, 5-dimethyl-2-norbornene, 1,4, 4a, 9, 9a, 10-heptahydro-9, 10[1 ', 2' ] -phenyl ring-1, 4-methanoanthracene, indanyl norbornene (i.e., the reaction product of 1,4, 4, 9-tetrahydro-1, 4-methanofluorene, CPD and indene), 6, 7, 10, 10-tetrahydro-7, 10-methanofluorene (i.e., the reaction product of CPD and acenaphthylene), 1,4, 4, 9, 9, 10-heptahydro-9, 10[1 ', 2' ] -benzene ring-1, 4-methanoanthracene, endo-5, 6-dimethyl-2-norbornene, endo, exo-5, 6-dimethyl-2-norbornene, exo-5, 6-dimethyl-2-norbornene, 1,4, 4,5, 6, 9, 10, 13, 14, 14-decahydro-1, 4-methanobenzocyclododecene (i.e., the reaction product of CPD and 1, 5, 9-cyclododecatriene), 2, 3, 3, 4, 7, 7-heptahydro-4, 7-methano-1H-indene (i.e., the reaction product of CPD and cyclopentene), 1,4, 4,5, 6, 7, 8, 8-octahydro-1, 4-methanonaphthalene (i.e., a reaction product of CPD and cyclohexene), 1,4, 4,5, 6, 7, 8, 9, 10, 10-decahydro-1, 4-methanobenzocyclooctene (i.e., a reaction product of CPD and cyclooctene), and 1, 2, 3, 3, 3, 4, 7, 7, 8, 8-decahydro-4, 7-methanocyclopenta [ a ] indene.

In another embodiment of the invention, the polymer may be crosslinked (latent crosslinked) in a post-polymerization curing step. In this embodiment, norbornene-type monomers containing pendant post-crosslinkable functional groups are copolymerized with the polycyclic backbone, whereupon the functional groups are subsequently crosslinked by well-known techniques. Post-crosslinkable functional groups means that the functional group is inert in the initial polymerization reaction, but it can undergo subsequent chemical reactions to effect crosslinking of adjacent polymer chains. Suitable postcrosslinkable monomers are represented by structure VII, wherein at least R¹～R⁴One of them being selected from linear or branched C₂～C₁₀Alkenyl radical, C₄～C₁₀CycloalkenesRadical, - (CH)₂)_nSi(OR⁵)₃Wherein n and R⁵As defined above, R¹And R²Or R³And R⁴May together represent C₁-C₁₀Alkylidene, condensed ring radicals, wherein R¹And R⁴Together with the two ring carbon atoms to which they are attached to form an unsaturated C₄～C₈And (4) a ring. In certain embodiments, post-crosslinkable alkenyl functionality includes vinyl, butenyl, and cyclohexenyl. In certain embodiments, alkylidene includes methylidene and ethylidene substituents. In certain embodiments, the alkoxysilyl group includes trimethoxysilyl and triethoxysilyl moieties. In certain embodiments, the crosslinking agent comprising a fused polycyclic system comprises dicyclopentadiene (DCPD) and an asymmetric trimer of Cyclopentadiene (CPD). Some illustrative latent crosslinking agents include, but are not limited to, the formulas given below:

and

wherein R is_hRepresents non-halogenated, halogenated and perhalogenated groups, e.g. C_nQ”_2n+1N is an integer of 1 to 10, and Q' represents hydrogen or halogen (e.g., Br, Cl or F).

The latent crosslinkable pendent groups can be reacted by a variety of known chemical agents capable of initiating the reaction of the functional groups. For example, with the above structure VII R¹～R⁵Defined alkenyl, cycloalkenyl and alkylidene groups may be crosslinked by a free radical mechanism, and alkoxysilyl groups may be crosslinked by a cationic reaction mechanism. Representative monomers containing post-crosslinkable functional groups are represented as follows:

in a latent crosslinking embodiment of the present invention, the crosslinking reaction step may be induced with a free radical initiator. Suitable initiators are those which can be activated thermally or photochemically. An initiator may be added to the reaction medium and polymerization of the monomer mixture allowed to proceed to completion. If latent initiators are present during the polymerization, the critical consideration is that the free-radical generating compounds used are stable (do not decompose) at the polymerization temperature of the monomer reaction medium. Alternatively, the latent initiator may be added to the polymer in solution in a suitable solvent after the polymerization is complete. When a thermally activated free-radical generator is used or embodiments use a photo-acid generator, latent crosslinking is induced by exposing the polymeric medium to a temperature above the decomposition temperature of the free-radical generating compound. In embodiments where a photoinitiated free radical generator is used, latent crosslinking is induced by exposing the polymeric medium to a light emitting source such as an e-beam and UV radiation. Suitable free radical generator compounds (crosslinking agents) include organic peroxides and aliphatic azo compounds. Aliphatic azo compounds are suitable initiators for both thermally and photochemically activated crosslinking embodiments of the present invention, while organic peroxides are only suitable as thermally activated initiators. The amount of cross-linking agent used is in the range of 0.005 to 5.0 parts by weight based on 100 parts by weight of monomer in the reaction medium.

Suitable organic peroxides include, but are not limited to, dibenzoyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, diacetyl peroxide, diisobutyryl peroxide, dilauroyl peroxide, t-butylperoxybenzoate, t-butyl peracetate, 2, 5-bis (benzoyl peroxide) -1, 2-dimethylhexane, di-t-butyl diperoxononanedioate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroctoate, 2, 5-bis (2-ethylperoxyhexanoyl) -2, 5-dimethylhexane, t-butyl peroxyneodecanoate, ethyl 3, 3-bis (t-butyl peroxy) butyrate, 2-bis (t-butyl peroxy) butane, 1-bis (t-butyl peroxy) cyclohexane, 1, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhex-3-yne, di-t-butyl peroxide, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, dicumyl peroxide, n-propyl peroxydicarbonate, isopropyl peroxydicarbonate, cyclohexyl peroxydicarbonate, and acetyl peroxydicarbonate.

Suitable azo compounds include, but are not limited to, 2,2 '-azobis [2, 4-dimethyl ] pentane, 2- (t-butylazo) -4-methoxy-2, 4-dimethylpentanenitrile, 2, 2' -azobis (isobutyronitrile), 2- (t-butylazo) -2, 4-dimethylpentanenitrile, 2- (t-butylazo) isobutyronitrile, 2- (t-butylazo) -2-methylbutanenitrile, 1-azobis-cyclohexanecarbonitrile, 1- (t-pentylazo) cyclohexanecarbonitrile, and 1- (t-butylazo) cyclohexanecarbonitrile.

Suitable photoinitiators for free radical crosslinking include, but are not limited to, benzoin ethyl ether, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, 4, 4 '-bis (diethylamino) benzophenone, 4, 4' -bis (dimethylamino) benzophenone, and 4- (dimethylamino) benzophenone.

Suitable photoinitiators for cationic crosslinking include, but are not limited to, onium salts, halogenated withExamples of the onium salt include unsubstituted, symmetrically or asymmetrically substituted alkyl, alkenyl, aralkyl, aromatic group, diazonium salt having heterocyclic group, ammonium salt, iodonium salt, sulfonium salt, phosphonium salt, arsonium salt, oxonium salt, etc. examples are boric acid, arsenic acid, phosphoric acid, antimonic acid, sulfuric acid, carboxylic acid and their halidesAromatic hydrocarbon compounds, halogen-containing aromatic compounds, other halogen-containing heterocyclic compounds, sulfonyl halides, and the like. Practical examples of the o-benzoquinone azido compound are 1, 2-benzoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, 1, 2-naphthoquinone diazide-6-sulfonate, 2, 1-naphthoquinone diazide-4-sulfonate, 2, 1-naphthoquinone diazide-5-sulfonate, 2, 1-naphthoquinone diazide-6-sulfonate, other quinone diazide derivative sulfonates, 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 1, 2-naphthoquinonediazido-6-sulfonyl chloride, 2, 1-naphthoquinonediazido-4-sulfonyl chloride, 2, 1-naphthoquinonediazido-5-sulfonyl chloride, 2, 1-naphthoquinonediazido-6-sulfonyl chloride, other quinonediazido derivative sulfonyl chlorides.

α -bis (sulfonyl) diazomethane Compoundsα -bis (sulfonyl) diazomethane, with alkyl, alkenyl, aralkyl, aromatic or heterocyclic groups, etc. α -carbonyl- α -sulfonyl diazomethane compounds are non-substituted or symmetrically or asymmetrically substituted α -carbonyl- α -sulfonyl diazomethane, with alkyl, alkenyl, aralkyl, aromatic or heterocyclic groups, sulfone compounds are non-substituted or symmetrically or asymmetrically substituted sulfone compounds or disulfone compounds, with alkyl, alkenyl, aralkyl, aromatic or heterocyclic groups, organic acid esters are non-substituted or symmetrically or asymmetrically substituted carboxylic acid esters, sulfonic acid esters, etc., with alkyl, alkenyl, aralkyl, aromatic or heterocyclic groups, organic amides are non-substituted or symmetrically or asymmetrically substituted carboxylic acid amide compounds, sulfonamide compounds, etc., with alkyl, alkenyl, aralkyl, aromatic or heterocyclic groups.

The decomposition temperatures of the aforementioned free radical generator compounds, when present in the polymerization process or in the polymerization medium, are well known in the art of the present process and can be selected depending on the initial reaction polymerization temperature used. In other words, the initiator compound must be stable at the polymerization temperature in order to be useful for the post-polymerization crosslinking reaction. As previously discussed, latent crosslinking may be performed thermally or photochemically.

As previously discussed, the trialkoxysilyl-containing monomer can be crosslinked by latent crosslinking in the presence of a cationic initiator. The polymerization-stable cationic initiator is heat-activatable to induce crosslinking of the silyl groups. Suitable cationic crosslinking initiators include, for example, dibutyltin dilaurate, dimethyltin dilaurate, dioctyltin dilaurate.

The total amount of multifunctional norbornene-type crosslinkable monomer and post-crosslinkable monomer optionally present in the reaction mixture may be in the range of 0.1 mole% to 50 mole%, based on the total amount of monomers in the monomer mixture used for the reaction. In one embodiment, the total amount of cross-linking agent is in the range of 1 mole% to 25 mole% of the total monomer mixture. In another embodiment, the total amount of crosslinking agent is in the range of 1 mole% to 10 mole% of the total monomer mixture.

Polymerization of monomers

The monomers of the invention are polymerized in solution or in bulk. The catalyst is added as a preformed single component catalyst to a reaction medium containing the desired monomer or the catalyst may be prepared in situ by mixing the procatalyst component, the group 15 electron donor component and the WCA salt activator component in the reaction medium. When the catalyst and the group 15 electron donor are positioned, the group 15 electron donor is not required to be used as an independent component. In a certain in situ embodiment, a coordination procatalyst component (e.g., containing the desired ligand) is mixed with a WCA salt activator component in the reaction medium. In another in situ embodiment, for example, a procatalyst component with or without a ligand is mixed in a reaction medium with a component containing the desired ligand and a WCA salt activator component. The procatalyst component is generally exemplified in the above preformed catalyst preparation equations (1) through (4). In certain embodiments, the procatalyst (based on a group 10 metal): a group 15 electron donor component: the molar ratio of WCA salt is 1: 1-10: 1-100. In another embodiment, the ratio is from 1: 1 to 5: 1 to 20, and in yet another embodiment, the ratio is from 1: 1 to 2: 1 to 5. In embodiments of the present invention where the procatalyst is coordinated with a group 15 electron donor ligand and/or a labile neutral electron donor ligand, the molar ratio of procatalyst (based on metal content) to WCA salt is from 1: 1 to 100. In another embodiment, the ratio is 1: 1 to 20. In yet another embodiment, the ratio is 1: 1 to 5. The order in which the various catalyst components are added to the reaction medium is not critical.

The polymers prepared by the process of the present invention are addition polymers of repeating units of polycyclic olefins linked by 2, 3-chain linkages. The repeating units are polymerized from polycycloolefin monomers or combinations of polycycloolefin monomers containing at least one norbornene-type moiety as described herein.

Solution process

In the solution process, the polymerization reaction may be carried out by adding a preformed catalyst solution or individual catalyst components to the cycloolefin monomer solution or the monomer mixture used for the polymerization. The total amount of monomers in the solvent is, in one embodiment, in the range of 10 to 50 wt.%. In another embodiment, the total amount of monomers in the solvent is in the range of 20 to 30 wt.%. After the single component catalyst or catalyst components are added to the monomer solution, the reaction medium is agitated (e.g., stirred) to ensure complete mixing of the catalyst and monomer components.

The polymerization temperature may vary from 0 ℃ to 150 ℃. In another embodiment, the polymerization temperature may range from 10 ℃ to 100 ℃. In yet another embodiment, the polymerization temperature may range from 20 ℃ to 80 ℃.

Examples of the solvent for the polymerization reaction include, but are not limited to, alkane and cycloalkane solvents such as pentane, hexane, heptane and cyclohexane, halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane and 1-chloropentane; aromatic solvents such as benzene, xylene, toluene, 1,3, 5-trimethylbenzene, chlorobenzene, anisole and o-dichlorobenzene, Freon 112 halocarbon solvents, water and mixtures thereof. In certain embodiments, the solvent is selected from the group consisting of cyclohexane, toluene, 1,3, 5-trimethylbenzene, dichloromethane, 1, 2-dichloroethane, and water.

When an aqueous polymerization medium is desired, the group 15 electron donor ligand or component may be selected from the water-soluble phosphines described above, although this is not strictly required. The polymerization can be carried out in suspension or emulsion. In suspension, the monomer is suspended in an aqueous medium containing a suspending agent selected from one or more water-soluble substances such as polyvinyl alcohol, cellulose ethers, partially hydrolyzed polyvinyl acetates or gels, and then carried out in the presence of the catalytic system of the invention.

Emulsion polymerization can be generally carried out by emulsifying monomers in water or a mixed solvent of water and an organic solvent miscible with water (e.g., methanol or ethanol). In certain embodiments, this is accomplished in the presence of at least one emulsifier. The emulsion polymerization is then carried out in the presence of the catalysts discussed herein. Emulsifiers include, for example, mixed acid soaps containing fats and rosin acids, alkyl sulfonate soaps, and oligonaphthalene sulfonate soaps.

Ontology method

In the bulk polymerization process of the present invention at least one monomer component (e.g., at least one cyclic olefin monomer) is polymerized using a catalyst system. In another embodiment, the catalyst system is used in the bulk polymerization process of the present invention to polymerize at least one monomeric crosslinking component (e.g., at least one cyclic olefin crosslinking monomer). In yet another embodiment, the bulk polymerization process of the present invention is a two-component monomer system (i.e., at least two cyclic olefin monomers, none, one, or both of which are crosslinking monomers) polymerized using a catalytic system. In yet another embodiment, the bulk polymerization process of the present invention is an at least three-component monomer system (i.e., at least two cyclic olefin monomers, at least one of which is a crosslinking monomer) polymerized using a catalytic system.

The term bulk polymerization refers to a polymerization reaction that is typically carried out in the substantial absence of a solvent. However, in some cases, a small portion of solvent is present in the reaction medium. The small amount of solvent may be incorporated into the reaction medium by the introduction of components of the catalytic system which are in some cases dissolved in the solvent. Solvents may also be used in the reaction medium to reduce the viscosity of the polymer at the end of the polymerization reaction to facilitate subsequent use and handling of the polymer. The total amount of solvent that may be present in the reaction medium ranges from 0 to about 20 percent based on the weight of monomers present in the reaction mixture. In another embodiment, the total amount of solvent that may be present in the reaction medium ranges from 0 to about 10 percent based on the weight of monomers present in the reaction mixture. In yet another embodiment, the total amount of solvent that may be present in the reaction medium ranges from 0 to about 1 percent based on the weight of monomers present in the reaction mixture. In certain embodiments, the solvent used is selected such that the catalytic system components are soluble therein. Examples of solvents include, but are not limited to, alkane and cycloalkane solvents such as pentane, hexane, heptane and cyclohexane; halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1-dichloroethane, 1, 2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane and 1-chloropentane; esters such as ethyl acetate, isoamyl acetate; ethers such as THF and diethyl ether; aromatic solvents such as benzene, xylene, toluene, 1,3, 5-trimethylbenzene, chlorobenzene, anisole and o-dichlorobenzene, Freon 112 halogenated hydrocarbon solvents; and mixtures thereof. In a certain embodiment, the solvent is selected from the group consisting of benzene, fluorobenzene, o-difluorobenzene, p-difluorobenzene, pentafluorobenzene, hexafluorobenzene, o-dichlorobenzene, chlorobenzene, toluene, o-, m-, and p-xylenes, 1,3, 5-trimethylbenzene, cyclohexane, ethyl acetate, THF, and dichloromethane.

The coordination procatalyst containing the group 15 electron donor ligand is prepared in solution and then added to the desired monomer or monomer mixture containing the dissolved WCA salt activator. The reaction mixture is mixed and then allowed to react for 1 minute to 2 hours. The reaction mixture may optionally be heated to a temperature in the range of from 20 ℃ to 200 ℃. The polymerization temperature is not particularly limited. In one embodiment, the polymerization temperature is in the range of from 20 ℃ to 120 ℃. In another embodiment, the polymerization temperature is in the range of from 20 ℃ to 90 ℃.

The polymerization reaction may be carried out under an inert atmosphere such as nitrogen or argon. Advantageously, however, it has been found that the components of the catalytic system of the invention are not sensitive to moisture and to oxygen, allowing less stringent operating and processing conditions. After the initial polymerization a polymer cement was obtained. The cement may be used on the desired substrate or injected into a mold and post cured to complete the polymerization reaction.

Without wishing to be bound by any theory of the invention, it is believed that post-curing is desirable from the standpoint of conversion of the monomer to polymer. In the bulk process, the monomer is essentially a diluent for the components of the catalytic system. As the monomer is converted to polymer, the monomer to polymer conversion reaches a plateau and cannot be higher (vitrification). This barrier to conversion occurs as the reaction medium is gradually converted to polymer due to the loss of reactivity. Thus, the components of the catalytic system and the unconverted monomers are gradually separated and are not reacted. It is well known that the diffusivity in a polymer decreases dramatically when the polymer transitions through the rubbery state to the glassy state. It is believed that post-curing at elevated temperatures increases the reactivity of the reactants in the matrix, allowing further conversion of the monomers to the polymer.

Post-curing of the polymers of the present invention is in one embodiment carried out at an elevated temperature for a period of time sufficient to achieve the desired degree of monomer to polymer conversion. In one embodiment, the post-cure cycle is carried out at a temperature in the range of about 100 ℃ to about 300 ℃ for about 1 hour to about 2 hours. In another embodiment, the post-cure cycle is conducted at a temperature in the range of about 100 ℃ to about 300 ℃ for about 0.5 hours to about 4 hours. In yet another embodiment, the post-cure cycle is carried out at a temperature in the range of about 125 ℃ to about 200 ℃ for 1 to 2 hours. In yet another embodiment, the post-cure cycle is carried out at a temperature in the range of about 140 ℃ to about 180 ℃ for 1 to 2 hours. The curing cycle may be carried out at a constant temperature or may be carried out at a gradually increasing temperature, for example, by gradually increasing the curing temperature from a minimum desired curing temperature to a maximum desired curing temperature over a time period required for the curing cycle. In one embodiment (A), the temperature ramp may be performed by a gradual increase in slope of the temperature-time curve from the minimum desired temperature to the maximum desired temperature in the curing segment. When the maximum temperature is reached in this embodiment, the maximum temperature may optionally be maintained for a desired time until a desired cure state is obtained. In another alternative embodiment (B), the ramping of the temperature may be performed according to a step-wise curve on a temperature-time curve. In this embodiment, the temperature ramp is performed in a stepwise manner, from the minimum desired curing temperature to the maximum desired curing temperature during the curing cycle. In another embodiment (C), post-curing may be performed by combining the post-curing embodiments (a and B), wherein the curing cycle comprises a combination of a step-by-step method and a ramp-up method, from the minimum desired curing temperature to the maximum desired curing temperature. In yet another embodiment (D and E), the curing cycle may follow a curve from a desired minimum curing temperature to a desired maximum curing temperature. In embodiment A, B, C, it should be noted that the temperature rise and slope change need not be fixed between the minimum and maximum cure temperatures. In other words, the increase and change may be altered when the desired maximum curing temperature is reached from the desired minimum temperature. The temperature ramp up curve of the curing link is shown as follows:

the ramping up of temperature during the curing cycle is beneficial because it reduces the potential for catalyst degradation and reduces the volatility of unconverted monomer.

In another embodiment, polymerization and post-curing are carried out together. In one embodiment, the polymerization/post-curing is carried out at a temperature in the range of about 20 ℃ to about 200 ℃ for 1 to 2 hours. In another embodiment, the polymerization/post-curing is carried out at a temperature in the range of about 125 ℃ to about 200 ℃ for 1 to 2 hours. In yet another embodiment, the post-cure cycle is carried out at a temperature in the range of about 140 ℃ to about 180 ℃ for 1 to 2 hours.

Alternatively, the polymerization/post-curing may be carried out at more than one temperature (i.e., within a certain temperature range). For example, the polymerization/post-curing may be carried out in a temperature range similar to that given immediately above. If polymerization/post-curing is carried out within a certain temperature range, the temperature at which polymerization/post-curing is carried out may vary according to the above discussion in conjunction with the ramping up of the temperature.

Optionally, the additives may include, but are not limited to, those selected from the group consisting of: pigments, dyes, nonlinear optical dyes, erbium complexes, praseodymium complexes, neodymium complexes, plasticizers, lubricants, flame retardants, adhesives, antioxidants (e.g., Irganox 1010, 1076, 3114, or Cyanox 1790), ultraviolet stabilizers, masking agents, odor absorbers, crosslinkers, synergists (e.g., Irgafos 168, dilauryl thiodipropionate, or combinations thereof), toughening and impact modifiers, polymeric and viscosity modifiers, and mixtures thereof (e.g., polyisobutylene, EPDM rubber, silicone oligomers, and mixtures thereof) may be added by mixing one or more of them in a monomer medium prior to initiating polymerization. The identity and relative amounts of these ingredients are well known to those skilled in the art and will not be discussed in detail herein.

Optional additives are used to enhance polymer handling, appearance and/or physical properties. For example, additives may be used to increase and modify the coefficient of thermal expansion, hardness, impact strength, dielectric constant, solvent resistance, color, optical properties, and odor, among other properties, of the polymer product. Viscosity modifiers are used to improve the viscosity and shrinkage of the monomer mixture prior to initiation of polymerization. Suitable viscosity modifiers include elastomers and the norbornene-based polymers of the present invention. Viscosity modifiers may be dissolved in the polymerizable monomers of the present invention to modify the viscosity of the monomer reaction mixture. As discussed above, crosslinking may occur during the initial polymerization of the monomer mixture or during a thermal or photochemical curing step following polymerization.

In certain embodiments, when a procatalyst is used in the bulk polymerization system of the present invention, the molar ratio of monomer to procatalyst (based on metal content) and WCA salt activator is in the range of from about 500,000: 1 to about 5,000: 1: 20. In another embodiment the molar ratio of monomer to procatalyst (based on metal content) and WCA salt activator is in the range of about 250,000: 1: 5 to about 20,000: 1: 10. In yet another embodiment, the molar ratio of monomer to procatalyst (based on metal content) and WCA salt activator is in the range of about 200,000: 1: 20 to about 100,000: 1.

Additional information on the above can be found in International patent application publication WO 00/20472, 6/2000, by BFGoodrich, and WO 00/34344, 6/2000, by BFGoodrich, both of which are incorporated herein by reference in their entirety.

Optical waveguide formulation

In certain embodiments, the polymer compositions used in the present invention defined by one or more of the structural formulas VII, VIIa, and VIIb above have from about 100 to about 100,000 repeating units. In another embodiment, the polymer compositions useful in the present invention defined by one or more of the structural formulas VII, VIIa, and VIIb above have from about 500 to about 50,000 repeating units. In yet another embodiment, the polymer compositions useful in the present invention as defined by one or more of the structural formulas VII, VIIa, and VIIb above have about 1,000 to about 10,000 repeating units.

In one embodiment, the waveguide is fabricated using a process disclosed below using at least two polyacrylates, polyimides, benzocyclobutenes, cyclic olefin polymers such that the refractive indices of the core material and the cladding material differ at 830nm (Δ n at 830 nm) by at least 0.00075 or greater for the core and cladding compared (i.e., at least 0.05% for a cladding having a refractive index of 1.5). That is, the refractive index of the polymeric core layer is at least 0.05% greater than the refractive index of the at least one polymeric cladding layer. If the waveguide is a three-layer waveguide, the cladding layers (upper and lower) may be different polymer layers, so long as both layers have a refractive index that is at least 0.05% less than the polymer used to make the core layer.

In another embodiment, when the waveguide is fabricated from cyclic olefin monomers, the core and cladding polymer formulations of the optical waveguides of the present invention comprise at least one cyclic olefin monomer (e.g., at least one norbornene monomer) and/or at least one crosslinking monomer, at least one procatalyst (see procatalyst discussion under the heading for preparation of catalysts above), at least one cocatalyst (i.e., a WCA salt having a weakly coordinating anion, see above), and optionally one or more additives discussed above (see discussion under the heading for bulk methods).

This mixture is polymerized by the bulk polymerization method discussed above (see discussion under the title of bulk method), either by adding the procatalyst to a mixture containing at least one cyclic olefin monomer, the cocatalyst and optional additives, or by adding the cocatalyst to a mixture containing at least one cyclic olefin monomer, the procatalyst and optional additives. In both cases, the active catalyst is generated in situ.

In another embodiment, each of the cladding and core formulations (differing in the degree of difference required to produce their respective refractive indices) are formed from a two-component system. That is, the coating formulation is derived from at least two components, component a and B. On the other hand, the core formulation is also produced from at least two components, components C and D. Each of the components A to D contains at least one norbornene-type monomer.

In another embodiment, components A and B are two substantially identical mixtures comprising at least one norbornene-type monomer and/or at least one crosslinking monomer. The difference between components A and B is generally due to the presence of a procatalyst in component A and a cocatalyst in component B. Other differences in components A and B may also exist. For example, component a may contain optional additives not contained in component B, and vice versa.

In certain embodiments, component a contains at least one norbornene-type monomer and/or at least one crosslinking monomer, at least one procatalyst and optional additives as discussed above (e.g., antioxidants). However, component B contains the same norbornene-type monomer, the same crosslinker, at least one cocatalyst and optionally additives (such as antioxidants) and/or synergists. In this case, the polymerization is carried out by bulk polymerization, mixing equal amounts of components a and B, thereby generating an active polymerization catalyst in situ.

Optionally, each core and/or cladding formulation may be a portion of a mixture in which at least one norbornene-type monomer and/or at least one crosslinking monomer, at least one cocatalyst and any optional additives are present. To facilitate the polymerization reaction, a procatalyst is added to the above mixture. In another embodiment, each core and/or cladding formulation may be a portion of a mixture in which at least one norbornene-type monomer and/or at least one crosslinking monomer, at least one procatalyst and any optional additives are present. To drive the polymerization reaction to take place, a cocatalyst is added to the above mixture. Again, it is noted that typically the at least one norbornene-type monomer and/or the at least one crosslinking monomer present in the clad and core formulations are different. In certain embodiments, it is this difference that allows the formation of polymers having different respective refractive indices.

In another embodiment, each of the overlay and/or core formulations comprises at least one norbornene-type crosslinking monomer (as discussed above), at least one cocatalyst, and any of the optional additives discussed above. To facilitate the polymerization reaction, a procatalyst is added to the above mixture. Alternatively, the above mixture may be divided into two or more portions and the cocatalyst added in one portion and the procatalyst added in the other portion. In this case, the polymerization is accomplished by a combination of all the portions.

In yet another embodiment, each of the clad and/or core formulations may be a portion of a mixture in which at least one norbornene-type crosslinking monomer, at least one procatalyst and any optional additives are present. To drive the polymerization reaction to take place, a cocatalyst is added to the above mixture. Again, it is noted that typically the at least one norbornene-type crosslinking monomer present in the clad and core formulations is different. In certain embodiments, it is this difference that allows the formation of polymers having different respective refractive indices. Alternatively, the above mixture may be divided into two or more portions and the cocatalyst added in one portion and the procatalyst added in the other portion. In this case, the polymerization is accomplished by a combination of all the portions.

The following are some illustrative coating and core formulations. It should be noted that these formulations are illustrative in nature and are not meant to be an exhaustive list of possible formulations for each of the cladding and core. Rather, other cladding and core formulations may be generated in view of the above disclosure, so long as the refractive index of the polymer prepared using the core formulation is at least 0.05% greater than the refractive index of the polymer prepared using the cladding formulation.

Exemplary coating formulations

In one embodiment, the coating formulation comprises: (1) containing C₄～C₂₀A norbornene monomer with an alkyl side chain, (2) a monomer containing C₁～C₁₀A norbornene-type monomer having an alkoxysilyl side chain, (3) at least one crosslinking agent (as disclosed above). In addition to components (1), (2) and (3), the coating formulation also contains at least one procatalyst, at least one cocatalyst and optional additives as discussed above. As noted above, if components (1), (2) and (3) are present in a mixture, then either the mixture contains no procatalyst or no cocatalyst and it is added later to the mixture.

Alternatively, components (1), (2) and (3) may be divided into two or more parts and procatalyst forming component a (which may optionally contain additives) is added in one part. In another part of components (1), (2) and (3) is added a co-catalyst forming component B (which may optionally contain the same, different or remaining additives as component A). In this embodiment, the polymerization is accomplished by the combination of all components A and B (together with the other parts of components (1), (2) and (3) not used for components A and B).

In certain embodiments, component (3) is at least one crosslinker selected from dimethyl bis (norbornenemethoxy) silane, octamethyl 1, 8-bis (norbornenemethoxy) tetrasiloxane, bis (norbornenemethyl) acetal, or fluoro crosslinkers (F-crosslinkers I and II as shown above).

Illustrative core formulations

In one embodiment, the core formulation comprises: (1) containing C₄～C₂₀A norbornene-type monomer having an alkyl side chain, (2) a norbornene-type monomer having a pendant silane group having at least one C group bonded to a silicon atom in the silane group₆～C₁₂Aryl groups, and (3) at least one cross-linking agent (as disclosed above). In addition to components (1), (2) and (3), the core formulation also contains at least one procatalyst, at least one cocatalyst and optionally an antioxidant and/or synergist. If components (1), (2) and (3) are present in a mixture, then either the mixture contains no procatalyst or no cocatalyst and it containsAnd later added to the mixture.

Alternatively, components (1), (2) and (3) may be divided into two or more parts and procatalyst forming component a (which may optionally contain additives such as antioxidants) is added in one part. In a further part of components (1), (2) and (3) is added a co-catalyst forming component B (which may optionally contain additives such as antioxidants and/or synergists).

In certain embodiments, component (3) is at least one crosslinker selected from dimethyl bis (norbornenemethoxy) silane, octamethyl 1, 8-bis (norbornenemethoxy) tetrasiloxane, bis (norbornenemethyl) acetal, or fluoro crosslinkers (F-crosslinkers I and II as shown above).

In one embodiment, the molar ratio of component (1) to component (2) to component (3) in the coating or core formulation, expressed in molar percentages, is 60-90: 5-20. In another embodiment, the molar ratio of component (1) to component (2) to component (3) is from 65-85: 7.5-20: 7.5-17.5. In yet another embodiment, the molar ratio of component (1) to component (2) to component (3) is 75-85: 10-20: 5-15.

Examples of crosslinking agents; and coating and core formulations:

the following examples are detailed descriptions of methods for making and using certain compositions of the present invention. The detailed preparation description is within the scope of the exemplification and serves the purpose of the illustrative, more generally described compositions and formulations set forth above.

Furthermore, in the following examples, lithium tetrakis (pentafluorophenyl borate). 2.5 etherate was denoted at a time as LiFeABA (see example Table 2), and (allyl) palladium (tricyclohexylphosphine) trifluoroacetate was expressed as allyl Pd-PCy₃TFA。

X. Preparation examples of selected crosslinking agents

Synthesis of (X1) dimethylbis (norbornenemethoxy) silane

Norbornene methanol (108.5g, 0.87mol.) was added dropwise to bis (dimethylamino) dimethylsilane (63.97g, 0.43mol.) in a reactor connected to a scrubber containing dilute hydrochloric acid. The reaction mixture was stirred for 4 hours. The mixture was then subjected to vacuum to remove the remaining amount of amine. Pure product was obtained by distillation under vacuum (117g, 90% yield).

The above reaction was also carried out using dimethyldichlorosilane instead of bis (dimethylamino) dimethylsilane.

To a vigorously stirred mixture of 5-norbornene methanol (50g, 0.40mol.), triethylamine (49g, 0.49mol.) and toluene (400mL) was added dropwise dimethyldichlorosilane (25.8g, 0.20 mol.). Stirring at room temperature resulted in the formation of a salt. The crude product was isolated by filtration of the salt, washing the toluene solution with water (3 times), followed by evaporation of the toluene. Distillation was performed under vacuum to give pure product (53g, 87% yield).

Synthesis of (X2) octamethyl 1, 8-bis (norbornenemethoxy) tetrasiloxane

Norbornene methanol (21.2g, 0.17mol.) was added dropwise to a solution containing octamethyldichlorosiloxane (30g, 0.085mol.), triethylamine (21g, 0.21mol.) and toluene (300 mL). The reaction mixture was stirred at room temperature for 8 hours. The solid formed (triethylamine hydrochloride) was filtered off. The toluene solution was then washed 3 times with a small amount of distilled water, and the toluene was removed to obtain a crude product. Distillation under vacuum gave pure product (39g, 87% yield).

Synthesis of (X3) bis (norbornenylmethyl) acetal

A mixture of norbornene methanol (100g, 0.81mol.), formaldehyde (. about.37%) (32.6g, 0.40mol.) and a catalytic amount of p-toluenesulfonic acid (0.2g) was heated at 100 ℃ in a flask directly connected to a dean-Stark trap. As the reaction proceeds, the amount of water in the trap increases. Within about 3 hours, the reaction was complete. Distillation under vacuum gave pure product (72.8g, 70% yield).

Examples of coating formulations (one component):

CL 1: coating formulations using octamethyl 1, 8-bis (norbornenemethoxy) tetrasiloxane

Lithium tetrakis (pentafluorophenyl borate). 2.5 etherate (0.0200g, 2.3X 10^-5mol.)Dissolved in a solvent containing hexyl norbornene (1)0g, 0.056mol.), octamethyl 1, 8-bis (norbornenemethoxy) tetrasiloxane (3.9g, 8.6mmol) and triethoxysilylnorbornene (2.9g, 0.011 mol.). 0.17g of Irganox 1076 (1% by weight) were added to the mixture.

To this mixture was added 0.16mL of a catalyst stock solution (3.02X 10)^-6mol.). (Note: preparation of stock solution by dissolving 0.01g of allylPd-PCy in 1mL of dry methylene chloride₃TFA。)

The curing/post-curing was carried out as follows: 10 minutes at 65 ℃ and 60 minutes at 160 ℃. When the monomer mixture was cured, a clear and good optical film was obtained.

CL 2: coating formulations using bis (norbornenylmethyl) acetal

Lithium tetrakis (pentafluorophenyl borate). 2.5 etherate (0.0042g, 4.8X 10^-6mol.) was dissolved in a monomer mixture containing hexyl norbornene (5g, 0.028mol.), bis (norbornenemethyl) acetal (1.57g, 6.1mmol) and triethoxysilyl norbornene (1.54g, 6.1 mmol). 0.08g Irganox 1076 (1% by weight) were added to the mixture.

To this mixture was added 0.08mL of a catalyst stock solution (1.6X 10)^-6mol.). (Note: preparation of stock solution by dissolving 0.01g of allylPd-PCy in 1mL of dry methylene chloride₃TFA。)

The curing/post-curing was carried out as follows: 10 minutes at 65 ℃ and 60 minutes at 160 ℃. When the monomer mixture was cured, a clear and good optical film was obtained.

CL 3: coating formulations using F-crosslinker I

Lithium tetrakis (pentafluorophenyl borate). 2.5 etherate (0.0061g, 6.9X 10^-6mol.) was dissolved in a monomer mixture containing hexyl norbornene (6.2g, 0.035mol.), F-crosslinker I (3.2g, 4.3mmol) and triethoxysilyl norbornene (1.11g, 4.3 mmol). 0.10g Irganox 1076 (1% by weight) was added to the mixture.

To this mixture was added 0.1mL of a catalyst stock solution (1.7X 10)^-6mol.). (Note: stock solution)Is prepared by dissolving 0.01g of allylPd-PCy in 1mL of dry methylene chloride₃TFA。)

The curing/post-curing was carried out as follows: 10 minutes at 65 ℃ and 60 minutes at 160 ℃. When the monomer mixture was cured, a clear and good optical film was obtained.

CL 4: coating formulations using F-crosslinker II

Lithium tetrakis (pentafluorophenyl borate). 2.5 etherate (0.0061g, 6.9X 10^-6mol.)Dissolved in a monomer mixture containing hexyl norbornene (6.2g, 0.035mol.), F-crosslinker II (3.6g, 4.3mmol) and triethoxysilyl norbornene (1.11g, 4.3 mmol). 0.10g Irganox 1076 (1% by weight) was added to the mixture.

To this mixture was added 0.1mL of a catalyst stock solution (1.7X 10)^-6mol.). (Note: preparation of stock solution by dissolving 0.01g of allylPd-PCy in 1mL of dry methylene chloride₃TFA。)

The curing/post-curing was carried out as follows: 10 minutes at 65 ℃ and 60 minutes at 160 ℃. When the monomer mixture was cured, a clear and good optical film was obtained.

Example of coating formulation (two-component) CL 5:

all monomers were degassed with dry nitrogen before use

And (2) component A:

to a mixture of hexyl norbornene (33g, 0.185mol.), triethoxysilyl norbornene (9.5g, 0.037mol.), and dimethyl bis (norbornenemethoxy) silane (7.5g, 0.0247mol.) was added allyl Pd-PCy dissolved in 0.2mL of methylene chloride₃TFA(0.0107g，1.98×10^-5mol.). To this mixture 0.50g of Irganox 1076 were added.

Component B

Lithium tetrakis (pentafluorophenyl borate). 2.5 etherate (0.0689g, 7.91X 10^-5mol.) was dissolved in a mixture of triethoxysilylnorbornene (9.5g, 0.037mol.) and dimethylbis (norbornenemethoxy) silane (7.5g, 0.0247 mol.). Once the solid has been completely dissolved, the solid,hexyl norbornene (33g, 0.185mol.) was added to the mixture. Irganox 1076(0.50g) was also added to the mixture and dissolved therein. In addition to the antioxidant, 0.25g of Irgafos 168 was added as a synergist.

Equal amounts of components a and B were mixed and cured. The curing/post-curing was carried out as follows: 10 minutes at 65 ℃ and 60 minutes at 160 ℃. When the monomer mixture was cured, a clear and good optical film was obtained.

The formulation of this example is shown in table 2 below.

TABLE 2
				Compound (I)	Components (A)(g)	Components B(g)	Total moles in A and B Number of
Hexyl norbornene	33	33	0.3708
				Triethoxysilyl group Norbornene based on carbon dioxide	9.5	9.5	0.0742
Dimethyl bis (norbornene) Methoxy) silanes	7.5	7.5	0.0493
				Total number of moles	N/A	N/A	0.0493
				LiFABA	N/A	0.0689	7.91×10-5mol.
Allyl Pd-PCy3TFA	0.0107	N/A	1.98×10-5mol.
Irganox® 1076	0.05	0.50
				Irgafos® 168	N/A	0.25

CO1. Example of core formulation (two components):

all monomers were degassed with dry nitrogen before use

And (2) component A:

in hexyl norbornene (31.5g, 0.18mol.), Diphenylmethylnorbornene methoxysilane (11.3g, 0.035mol.) and dimethylbis (norbornene methoxy) silane (7.5g, 0.025mol.) allyl Pd-PCy dissolved in 0.2mL of methylene chloride was added₃TFA(0.0102g，1.89×10^-5mol.). To this mixture 0.50g of Irganox 1076 were added.

Component B

Lithium tetrakis (pentafluorophenyl borate). 2.5 etherate (0.0658g, 7.55X 10^-5mol.) was dissolved in a mixture of diphenylmethyl (norbornenemethoxy) silane (11.3g, 0.035mol.) and dimethylbis (norbornenemethoxy) silane (7.5g, 0.0247mol.) and hexyl norbornene (31.5g, 0.18 mol.). Irganox 1076(0.50g) was also added to the mixture and dissolved therein. In addition to the antioxidant, 0.25g of Irgafos 168 was added as a synergist.

Equal amounts of components a and B were mixed and cured. The curing/post-curing was carried out as follows: 10 minutes at 65 ℃ and 60 minutes at 160 ℃. When the monomer mixture was cured, a clear and good optical film was obtained.

The formulation of this example is shown in table 3 below.

TABLE 3
				Compound (I)	Components (A)(g)	Component B (g)	Total moles in A and B Mole number
Hexyl norbornene	31.5	31.5	0.3539
				Diphenylmethyl (norborneol) Alkenylmethoxy) silanes	11.3	11.3	0.0706
Dimethyl bis (norbornene) Methoxy) silanes	7.2	7.2	0.0474
				Total number of moles	N/A	N/A	0.04719
				LiFABA	N/A	0.0658	7.55×10-5mol.
Allyl Pd-PCy3TFA	0.0102	N/A	1.89×10-5mol.
Irganox® 1076	0.05	0.50
				Irgafos® 168	N/A	0.25

Method for curing cycloolefin monomers

Formulation and fabrication of waveguides

Curing/post-curing

As discussed above under the heading of the bulk method, the monomer formulations of the present invention polymerize at a temperature of about 20℃ to about 200℃ for a time period of about 1 minute to about 2 hours. In another embodiment, the polymerization occurs at a temperature of from about 20 ℃ to about 120 ℃ for a period of from about 1 to about 40 minutes. In yet another embodiment, the polymerization occurs at a temperature of from about 40 ℃ to about 80 ℃ for a period of from about 5 to about 20 minutes. As noted above, the polymerization may be conducted under an inert atmosphere such as nitrogen or argon. In another embodiment, the polymerization may be conducted in a forced air, fume hood.

After polymerization, the polymer may be subjected to a post-curing step. In certain embodiments, the post-cure step is carried out at a temperature in the range of from about 100 ℃ to about 300 ℃ for about 1 to about 2 hours (as noted above, the temperature during post-cure may increase over time). In yet another embodiment, the post-curing step is carried out at a temperature in the range of from about 100 ℃ to about 300 ℃ for a period of time in the range of from about 0.5 to about 4 hours. In yet another embodiment, the post-curing step is carried out at a temperature in the range of from about 125 deg.C to about 200 deg.C for a period of from about 1 to about 2 hours. In yet another embodiment, the post-curing step is carried out at a temperature in the range of about 140 ℃ to about 180 ℃ for about 1 to about 2 hours.

Partial/cure/post cure

In another embodiment, at least one of the monomer formulations (e.g., either the core composition or the coating composition) is partially polymerized (cured) to a gel point at a temperature of from about 20 ℃ to about 120 ℃ for from about 0.1 to about 10 minutes. In yet another embodiment, the polymerization occurs at a temperature of from about 40 ℃ to about 100 ℃ for from about 1 to about 8 minutes. In yet another embodiment, the polymerization occurs at a temperature of from about 50 ℃ to about 70 ℃ for from about 2 to about 6 minutes. As noted above, the polymerization may be conducted under an inert atmosphere such as nitrogen or argon. In another embodiment, the polymerization may be conducted in a forced air, fume hood.

After partial curing, at least one further monomer formulation (uncured) may be placed on top of or over the partially cured monomer formulation. In certain embodiments, if at least one core composition is partially cured, at least one coating composition is disposed on top of the at least one core composition. In another embodiment, if the at least one coating composition is partially cured, then at least one core composition is placed on top of the at least one coating composition. In yet another embodiment, the at least one monomer formulation disposed on the at least one partially cured monomer formulation may be an otherwise similar formulation (i.e., another at least one core formulation disposed on the at least one partially cured monomer formulation).

When the desired monomer formulation combination is produced (at least one of which is partially cured as discussed above), the combination is cured at a temperature of from about 20 ℃ to about 200 ℃ for a period of time of from about 1 minute to about 2 hours. In another embodiment, the polymerization occurs at a temperature of from about 20 ℃ to about 120 ℃ for from about 1 to about 40 minutes. In yet another embodiment, the polymerization occurs at a temperature of from about 40 ℃ to about 80 ℃ for from about 5 to about 20 minutes. As noted above, the polymerization may be conducted under an inert atmosphere such as nitrogen or argon. In another embodiment, the polymerization may be conducted in a forced air, fume hood.

After the monomer combination is cured (polymerized), the polymer combination may be subjected to a post-curing step. In certain embodiments, the post-cure step is carried out at a temperature in the range of from about 100 ℃ to about 300 ℃ for about 1 to about 2 hours (as noted above, the temperature during post-cure may increase over time). In yet another embodiment, the post-curing step is carried out at a temperature in the range of from about 100 ℃ to about 300 ℃ for a period of time in the range of from about 0.5 to about 4 hours. In yet another embodiment, the post-curing step is carried out at a temperature in the range of from about 125 deg.C to about 200 deg.C for a period of from about 1 to about 2 hours. In yet another embodiment, the post-curing step is carried out at a temperature in the range of about 140 ℃ to about 180 ℃ for about 1 to about 2 hours.

Method for manufacturing waveguide

Coatings take precedence (Clad First)

Conventional molding methods for fabricating waveguides use cladding-first approach. For example, a general method of manufacturing a waveguide 1 is shown in fig. 1. First, in a molding method such as an injection molding method, a hot embossing method, and a reaction casting method, the coating film 12 (under-coating) is formed by casting on the template 10 (a nickel template or other suitable template) (see fig. 1(a)), and then cured. The lower cladding layer 12 is removed from the template 10 (see fig. 1(b)), and a liquid core material 14 is applied to the featured surface of the cladding layer 12 and forced into the groove by pressure, for example, using a doctor blade 16 (see fig. 1 (c)). Thereafter, the liquid core material 14 is cured and forms the ribbed waveguide structure 14a (see fig. 1 (d)). It should be noted that the waveguide structure depicted in fig. 1 is a ribbed structure. However, any suitable waveguide structure may be formed (e.g., mesh, format, slab, buried channel, etc.). An upper cladding layer 18 is then formed over a portion or the entire waveguide structure 14a by depositing a liquid cladding material that solidifies to form upper cladding layer 18 (see fig. 1 (e)).

Alternatively, upper cladding layer 18 may be formed separately rather than polymerized from a liquid formulation disposed over waveguide structure 14a and optionally a portion of lower cladding layer 12. In this embodiment, upper cladding layer 18 may be joined to the exposed portion of waveguide structure 14a by a suitable adhesive joining method (e.g., a layer of liquid cladding material that is a glue).

In another embodiment, the process of fig. 1 may be paused after step (d) is completed. In this case, a two-layer waveguide is obtained instead of the three-layer waveguide discussed above.

Using one of the cladding-first methods described above, a two-layer or three-layer waveguide product is obtained as a result. In addition, this conventional cladding-first method can produce various waveguide structures, such as buried rib-arranged waveguides, as shown in fig. 2A to 2C. Careful balancing of the dimensions of the ribbed waveguide (height, width, spacing and thickness of slab regions), with core and cladding index differences and control of the operating wavelength, can produce a waveguide structure in which light is well enclosed (fig. 2B and 2C).

It should be noted that the core/cladding compositions disclosed herein may be used in other existing waveguide fabrication processes (e.g., micro-molding/embossing; reactive ion etching; UV laser and e-beam writing; photochemical mapping; photo-bleaching; induced dopant diffusion; (photo-induced dopant diffusion, photo-pinning and selective polymerization); electric field induced selective reduction of electro-optically active molecules; polymerization of self-assembled prepolymers).

In addition, the template used in this embodiment may have a waveguide structure with channels that are actually larger than the final desired product. This feature allows for the application of a non-adherent coating (e.g., PTFE) or release agent on the template to facilitate removal of the lower cladding layer 12 from the template 10. Alternatively, separation of the lower cladding from the die plate 10 may be facilitated by flushing cold water over the lower cladding.

Core-First (Core-First) method:

using the core first approach discussed below, waveguides can be formed and even isolated buried channel waveguides. For purposes of discussion, the discussion of this method will refer to isolating buried channel waveguides. However, it is within the scope of the present invention to fabricate other waveguide structures, such as ribbed structures.

The manufacturing steps of the core-first method are performed in the reverse order compared to the conventional cladding-first method, as shown in fig. 3. The general procedure is described below. The core material mixture 30 is poured onto the surface of a template 32 (e.g., Ni, Si template, etc.) having recesses 34, the recesses 34 forming the shape and dimensions of the desired waveguide pre-structure (see (a) and (b)). For example, the isolation buried channel waveguide structure has a channel width of 1-200 μm and a height of 1-200 μm. However, any desired width and height may be achieved, so long as the channels are not too wide or too narrow when receiving the core material.

The scraper 36 rests directly on the template surface (at the location where the buried structure is desired) and serves to scrape off excess liquid core material mixture 30 (see fig. 3 (b)). The core material 30 remaining in the recess is then cured and forms at least one waveguide structure 30 a. If the core structure 30 is one of the core materials described above, the core material 30 may be cured according to any of the methods described above.

After the core material 30 remaining in the recess is fully cured, as described above (see fig. 3(c)), the cladding material mixture 38 is poured over the core-containing template, covering at least one exposed surface of the waveguide structure 30 a. The thickness of the lower cladding layer is also controlled with a doctor blade 36 (see fig. 3 (d)). After curing under suitable conditions, a lower cladding layer 40 is formed which is in contact with at least one surface of the waveguide structure (see fig. 3 (e)). The lower cladding layer 40/waveguide structure 30a combination is then removed from template 32 and inverted with the lower cladding layer on the bottom (see fig. 3 (f)).

In certain embodiments, the thickness of the lower cladding layer is sufficient to allow the lower cladding layer 40 and waveguide structure 30a to be removed from the template 32 without damage. In another embodiment, the thickness of each of the overlays (lower and upper) is from about 2 to about 20,000 μm or from about 4 to about 20,000 μm in total. In yet another embodiment, the thickness of each coating layer is from about 10 to about 10,000 μm or from about 20 to about 10,000 μm in total. Note that the defined height of the upper cladding layer includes the height of the core layer (see fig. 3 (h)).

Next, an over-clad material 42 is applied to the core layer surface of the film and its thickness is also controlled with a doctor blade 36 (see fig. 3 (g)). Subsequently, the upper cladding material 42 is cured to form an upper cladding layer 42 a. Upon completion of the solidification process of the upper cladding layer, the waveguide 50 is formed (see fig. 3 (h)). It should be noted that curing of the third layer results in a three-layer polymer film containing the isolated channel waveguide core 30a buried between the lower cladding layer 40 and the upper cladding layer 42 a.

Optionally, if a two-layer optical waveguide is desired, pausing the step (f) after completion of the step.

In addition, the template used in this embodiment may have a core structure that is actually larger than that of the final desired product. This feature allows for the application of a non-adherent coating (e.g., PTFE) or release agent on the template to facilitate removal of the cored structure 30a and lower cladding layer 40 from the template 32. Optionally, separation of the lower cladding from the die plate may be facilitated by flushing cold water over the lower cladding.

This core-first method produces the core structure of the waveguide by casting a template (e.g., Ni or Si) that does not interact with the liquid core precursor, as compared to the cladding-first method. The improvement in the fabrication method allows for complete removal of the core layer regions and enables easy filling of the channels with a low viscosity core prepolymer mixture which simplifies fabrication of the isolated buried channel waveguide.

Optical micrographs of two-layer and three-layer waveguide structure samples fabricated using the core-first method are shown in fig. 4A-4D, and in one embodiment, the cyclic olefin compositions discussed previously (e.g., using the core and cladding formulations discussed above). The waveguides of fig. 4A-4D were fabricated using the cladding compositions detailed in table 2 above and the core compositions detailed in table 3 above. FIG. 4A shows a two-layer isolated channel waveguide structure; FIG. 4B shows a three-layer buried channel waveguide structure; FIG. 4C is a schematic illustration of a side view of the waveguide arrangement of FIG. 4B (dimensions 13 μm wide, 16 μm high, 13 μm apart) with input optical fiber positions indicated by dark circles; fig. 4D is a photograph of the waveguide output when diode laser light (λ 820nm) is coupled with the single core structure 30a shown in fig. 4C. The output pattern shows that the waveguides are multimode at 820nm and there is no cross-coupling between adjacent waveguides.

The core-first method may also be used with any suitable polymer system, including, but not limited to, polyacrylates (such as deuterated polyfluoromethylacrylates), polyimides (such as cross-linked polyimides or fluorinated polyimides), or benzocyclobutenes.

In view of fig. 5A-5B, these figures depict the condition "swell". "swelling" may occur during cladding-first processes for forming waveguides (see FIG. 1). While not wishing to be bound by any theory, it is believed that swelling occurs during the polymerization of the core composition in the previously polymerized underlying skin structure. In some instances, "swelling" may be undesirable. Thus, the use of, for example, the core-first approach described above to manufacture a waveguide (see fig. 3) may reduce and/or eliminate such "bulging". This is shown by comparing fig. 5A (manufactured using the cladding priority method described above) with fig. 5B (manufactured using the core priority method described above).

Improved core priority:

in another embodiment, the above-described core-first process may be modified to utilize the partial cure/post cure polymerization process discussed above (see above). For purposes of discussion, the discussion of this method will refer to isolating buried channel waveguides. However, it is within the scope of the present invention to make other channel structures, such as ribbed structures.

This improved core priority will be discussed with respect to fig. 6, 7A and 7B. Referring to fig. 6, generally the improved core priority method is described as follows. The core material mixture 60 is poured onto the surface of a template 62 (e.g., Ni, Si template, etc.) having grooves 64, the grooves 64 forming the shape and dimensions of the desired waveguide pre-structure (see (a) and (b)). For example, the isolation buried channel waveguide structure has a channel width of 1-200 μm and a height of 1-200 μm. However, any desired width and height may be achieved, so long as the channels are not too wide or too narrow when receiving the core material.

The scraper 66 rests directly on the template surface (at the location where the buried structure is desired) and serves to scrape off excess liquid core material mixture 60 (see fig. 6 (b)). Next, the core material 60 remaining in the recess is partially cured and forms at least one pre-waveguide structure 60 a. If the core material 60 is one of the above-described core materials, the core material 60 may be partially cured according to the partial cure/post-cure method described above.

After the core material 60 remaining in the recess is partially cured, as described above (see fig. 6(c)), the cladding material mixture 68 is poured onto the template containing the core layer, covering at least one exposed surface of the waveguide structure 60 a. The thickness of the lower cladding layer is also controlled with a doctor blade 66 (see fig. 6 (d)). After curing under suitable conditions (see discussion above under partial cure/post-cure), a lower cladding layer 70 is formed which is in contact with at least one surface of the waveguide structure (see fig. 6 (e)). The lower cladding layer 70/waveguide structure 60a combination is then removed from template 62 and inverted with the lower cladding layer in the lower portion (see fig. 6 (f)).

In certain embodiments, the thickness of the lower cladding layer is sufficient to allow the lower cladding layer 70 and waveguide structure 60a to be removed from the template 62 without damage. In another embodiment, the thickness of each of the overlays (lower and upper) is from about 2 to about 20,000 μm or from about 4 to about 20,000 μm in total. In yet another embodiment, the thickness of each coating layer is from about 10 to about 10,000 μm or from about 20 to about 10,000 μm in total. Note that the defined height of the upper cladding layer includes the height of the core layer (see fig. 6 (h)).

Next, an overlying layer material 72 is applied to the core surface of the film and its thickness is also controlled with the doctor blade 66 (see FIG. 6 (g)). Subsequently, the upper cladding material 72 is cured to form an upper cladding layer 72 a. Upon completion of the solidification process of the upper cladding layer, the waveguide 75 is formed (see fig. 6 (h)). It should be noted that curing of the third layer results in a three-layer polymer film containing the isolated channel waveguide core 60a buried between the lower cladding layer 70 and the upper cladding layer 72 a.

Optionally, if a two-layer optical waveguide is desired, pausing the step (f) after completion of the step.

In addition, the template used in this embodiment may have a core structure that is actually larger than that of the final desired product. This feature allows for the application of a non-adherent coating (e.g., PTFE) or release agent on the template to facilitate removal of the cored structure 60a and lower cladding layer 70 from the template 62. Optionally, separation of the lower cladding from the die plate may be facilitated by flushing cold water over the lower cladding.

This modified core-first process also produces the core structure of the waveguide by casting a template (e.g., Ni or Si) that does not interact with the liquid core precursor, as compared to the cladding-first process. The improvement in the fabrication method allows for complete removal of the core layer regions and enables easy filling of the channels with a low viscosity core prepolymer mixture which simplifies fabrication of the isolated buried channel waveguide. In addition, the improved core-first method reduces the curing time required to fabricate the waveguide and reduces the amount of evaporation of the liquid core layer during curing, thereby producing a fully filled buried waveguide structure. Optical micrographs of samples of the two-layer waveguide structure fabricated using the core-first method (fig. 7A) and the modified core-first method (fig. 7B) confirm that the modified core-first method allows the formation of a fully filled buried waveguide structure.

Multilayer cutting method

As shown in FIG. 8, a two-layer polymer film 80, having a thin layer 82 (e.g., 25 μm) of core material over a thick layer 84 (e.g., 100 μm thick) of lower cladding material, can be readily fabricated in a conventional film casting process. These layers may also be thicker or thinner than discussed with respect to the layer thickness of the core priority method.

Next, the template 86 having design features 88a or 88b is used here to form the modified core layer 82a or 82b having openings 90a or 90b therein. As shown in fig. 8, the opening 90a or 90b in the modified core layer 82a or 82b penetrates through the core layer 82 and into the lower cladding layer 84. In this method, the formation of the core and cladding features is accomplished by a suitable cutting technique (e.g., hot embossing, diamond milling, laser ablation, or Reactive Ion Etching (RIE), etc.). After the modified core layer 82a or 82b is formed, an overlayer is formed by applying an overlayer material to a two-layer polymer film having a modified core layer 82a or 82b with an opening 90a or 90 b. The overburden material is cured by a suitable method to produce overburden 92. During the formation of the upper cladding layer 92, an upper cladding material is filled within the openings 90a or 90b to complete the preparation of the buried waveguides 94a or 94 b.

Buried waveguides 94a or 94b comprise a separate core structure sandwiched, or otherwise enclosed, or otherwise buried between lower and upper cladding materials. These waveguides can be used as basic components for integrated optical circuits in the optoelectronic market.

In another embodiment, a three layer polymer film (i.e., a clad-core-clad multilayer film) is used to fabricate a waveguide according to the method detailed in fig. 8.

This method of manufacture can be used not only with the cyclic olefin monomer compositions discussed herein, but also with other polymer systems such as polyacrylates (e.g., deuterated polyfluoromethacrylates), polyimides (e.g., crosslinked polyimides or fluorinated polyimides), or benzocyclobutenes. In addition, other polymers may also be used. These polymers include, but are not limited to, thermally curable, bulk polymerizable materials, photo-curable polymers, and solution-based polymeric materials.

FIGS. 9A-9D are additional embodiments of waveguides prepared using a multilayer cutting process and the core/cladding formulations described above. FIG. 9A is an optical micrograph of a two-layer isolated channel waveguide made using a multilayer cutting process; fig. 9B depicts laser light (λ 820nm) from a diode applied to the waveguide intermediate isolation channel structure of fig. 9A; FIG. 9C is a three layer isolated buried channel waveguide prepared from a two or three layer structure prepared using a multilayer cutting process and coating the structure with a cladding material; fig. 9D depicts laser light (λ 820nm) from a diode applied to the waveguide intermediate isolation buried channel structure in fig. 9C. It should be noted that when the photographs of fig. 9B-9D were taken, the intensity of the light input from the diode laser was maximized to determine if there was any crosstalk between the isolated buried waveguide structures. As shown in fig. 9B-9D, the output pattern shows no cross-coupling between adjacent waveguide structures.

Although the invention has been shown and described with respect to certain preferred embodiments, it is obvious that equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this patent specification and the annexed drawings. In particular regard to the various functions performed by the above described integers (components, assemblies, devices, compositions, etc.), the terms (including a reference to a "means") used to describe such integers are intended to correspond, unless otherwise indicated, to the integer or integers which perform the specified function of the integer or integers (i.e., that are functionally equivalent). And even not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiments of the invention. In addition, while a particular feature of the invention may have been discussed above with respect to only one of several illustrated embodiments, such feature may be combined with one or more other features of the other embodiments as may be desired and advantageous for any given or particular application.

Claims (51)

1. A polycyclic polymeric composition formed from one or more monomers or oligomers represented by the following structure:

wherein each X' independently represents oxygen, nitrogen, sulfur or a compound of the formula- (CH)₂)_n′-methylene, wherein n' is an integer from 1 to 5; "a" represents a single or double bond; r¹～R⁴Independently represents hydrogen, a hydrocarbyl group or a functional substituent; m is an integer of 0 to 5, with the proviso that when "a" is a double bond, R¹、R²One and R³、R⁴One of which is not present.

2. The polymer composition of claim 1, provided that R¹～R⁴Any of which is a hydrocarbyl group, then R¹～R⁴Independently comprise a hydrocarbyl, halogenated hydrocarbyl or perhalogenated hydrocarbyl group selected from: i) linear or branched C₁～C₁₀An alkyl group; ii) linear or branched C₂～C₁₀An alkenyl group; iii) Linear or branched C₂～C₁₀An alkynyl group; iv) C₄～C₁₂A cycloalkyl group; v) C₄～C₁₂A cycloalkenyl group; vi) C₆～C₁₂An aryl group; and vii) C₇～C₂₄An aralkyl group.

3. The polymer composition of claim 1, wherein X' "is hydrogen or C₁～C₁₀Nitrogen of the alkyl group.

4. The polymer composition of claim 1, wherein R¹And R²Or R³And R⁴Together represent C₁～C₁₀An alkylidene group.

5. RightsThe polymer composition of claim 1, wherein R¹～R⁴One or more of which represent functional substituents independently selected from

-(CH₂)_n-CH(CF₃)₂-O-Si(Me)₃，-(CH₂)_n-CH(CF₃)₂-O-CH₂-O-CH₃，

-(CH₂)_n-CH(CF₃)₂-O-C(O)-O-C(CH₃)₃，-(CH₂)_n-C(CF₃)₂-OH，-(CH₂)_nC(O)NH₂，

-(CH₂)_nC(O)Cl，-(CH₂)_nC(O)OR⁵，-(CH₂)_n-OR⁵，-(CH₂)_n-OC(O)R⁵，-(CH₂)_n-C(O)R⁵，

-(CH₂)_n-OC(O)OR⁵，-(CH₂)_nSi(R⁵)₃，-(CH₂)_nSi(OR⁵)₃，-(CH₂)_n-O-Si(R⁵)₃And are and

-(CH₂)_nC(O)OR⁶，

wherein n independently represents an integer of 0 to 10, R⁵Independently represent hydrogen, linear or branched C₁～C₂₀Alkyl, linear or branched C₁～C₂₀Halogenated or perhalogenated alkyl, linear or branched C₂～C₁₀Alkenyl, linear or branched C₂～C₁₀Alkynyl, C₅～C₁₂Cycloalkyl radical, C₆～C₁₄Aryl radical, C₆～C₁₄Halogenated or perhalogenated aryl and C₇～C₂₄Aralkyl group; r⁶Is selected from-C (CH)₃)₃、-Si(CH₃)₃、-CH(R⁷)OCH₂CH₃、-CH(R⁷)OC(CH₃)₃Or one of the following cyclic groups:

or one of the following:

and

wherein R is⁷Represents hydrogen or linear or branched (C)₁～C₅) An alkyl group.

6. The polymer composition of claim 4, wherein R⁵Is a halogenated or perhalogenated group.

7. The polymer composition of claim 1, wherein R¹、R⁴And together with the two ring carbon atoms to which they are attached, represent a substituted or unsubstituted cycloaliphatic radical containing from 4 to 30 ring carbon atoms or a substituted or unsubstituted aryl radical containing from 6 to 18 ring carbon atoms or combinations thereof.

8. The polymer composition of claim 6, wherein the cycloaliphatic radical is a mono-or polycyclic cycloaliphatic radical.

9. The polymer composition of claim 7, wherein the cycloaliphatic radical is mono-unsaturated or poly-unsaturated.

10. The polymer composition of claim 1, wherein the composition is a homopolymer.

11. The polymer composition of claim 1, wherein the composition is a copolymer comprising at least two different repeat units according to claim 1.

12. The polymer composition of claim 1 wherein the number of repeat units in the composition is from about 100 to about 100,000.

13. The polymer composition of claim 1 wherein the number of repeat units in the composition is from about 500 to about 50,000.

14. The polymer composition of claim 1 wherein the number of repeating units in the composition is from about 1,000 to about 10,000.

15. The polymer composition of claim 1, wherein the polymer composition is prepared from one or more monomers or oligomers according to claim 1 in combination with one or more crosslinking agents.

16. The polymer composition of claim 15, wherein the crosslinking agent is selected from at least one of the following structures:

wherein Y represents a methylene group (-CH)₂-) and m independently represent an integer of 0 to 5, and when m is 0, Y represents a single bond; a linked polycyclic crosslinker as shown in structure VIII below:

wherein "a" independently represents a single bond or a double bond, m independently represents an integer of 0 to 5, R⁹Is a divalent group selected from divalent hydrocarbon groups, divalent ether groups and divalent silyl groups, and n is equal to 0 or 1; or a crosslinking agent as shown below:

wherein n is 1 to 4.

17. The polymer composition of claim 15, wherein the crosslinking agent is selected from at least one of the following structures:

and

18. the polymer composition of claim 15, wherein the crosslinking agent is selected from at least one of the following structures:

wherein m and n, if present, are independently integers from 1 to 4.

19. The polymer composition of claim 15, wherein the crosslinking agent is selected from at least one of the following structures:

and

20. the polymer composition of claim 15, wherein the crosslinking agent is a latent crosslinking agent.

21. The polymer composition of claim 20 wherein the latent cross-linking agent is selected from one or more of the following compounds:

and

wherein R is_hRepresents a non-halogenated, halogenated or perhalogenated group, e.g. C_nQ”_2n+1N is an integer of 1 to 10, and Q' represents hydrogen or halogen.

22. A polycyclic polymeric composition formed from one or more monomers or oligomers represented by the following structure:

wherein each X' independently represents oxygen, nitrogen, sulfur or a compound of the formula- (CH)₂)_n′Of (A) toA methylene group, wherein n' is an integer of 1 to 5; q represents an oxygen atom or a group N (R)⁸)；R⁸Selected from hydrogen, halogen, linear or branched C₁～C₁₀Alkyl and C₆～C₁₈Aryl, m is an integer of 0 to 5.

23. The polymer composition of claim 22, wherein the composition is a homopolymer.

24. The polymer composition of claim 22, wherein the composition is a copolymer.

25. The polymer composition of claim 22, wherein X' "is hydrogen or C₁～C₁₀Nitrogen of the alkyl group.

26. The polymer composition of claim 22 wherein the number of repeat units in the composition is from about 100 to about 100,000.

27. The polymer composition of claim 22 wherein the number of repeat units in the composition is from about 500 to about 50,000.

28. The polymer composition of claim 22 wherein the number of repeat units in the composition is from about 1,000 to about 10,000.

29. The polymer composition according to claim 22, wherein the polymer composition is prepared from one or several monomers or oligomers according to claim 22 in combination with one or several cross-linking agents.

30. The polymer composition of claim 29, wherein the at least one crosslinking agent is selected from one or more of the following compounds:

wherein Y represents a methylene group (-CH)₂-) and m independently represent an integer of 0 to 5, and when m is 0, Y represents a single bond; as shown in Structure VIII belowThe bonded polycyclic crosslinkers shown:

wherein "a" independently represents a single bond or a double bond, m independently represents an integer of 0 to 5, R⁹Is a divalent group selected from divalent hydrocarbon groups, divalent ether groups and divalent silyl groups, and n is equal to 0 or 1; or a crosslinking agent as shown below:

wherein n is 1 to 4.

31. The polymer composition of claim 29, wherein the at least one crosslinking agent is selected from one or more of the following compounds:

and

32. the polymer composition of claim 29, wherein the at least one crosslinking agent is selected from one or more of the following compounds:

wherein m and n, if present, are independently integers from 1 to 4.

33. The polymer composition of claim 29, wherein the at least one crosslinking agent is selected from one or more of the following compounds:

and

34. the polymer composition of claim 29, wherein the crosslinking agent is a latent crosslinking agent.

35. The polymer composition of claim 34 wherein the latent cross-linking agent is selected from one or more of the following compounds:

and

wherein R is_hRepresents a non-halogenated, halogenated or perhalogenated group, e.g. C_nQ”_2n+1N is an integer of 1 to 10, and Q' represents hydrogen or halogen.

36. A polycyclic polymer composition formed from one or more monomers represented by the following structure:

wherein X' "represents oxygen, nitrogen, sulfur or has the formula- (CH)₂)_n′-methylene, wherein n' is an integer from 1 to 5; r^DIs deuterium, "i" is an integer of 0 to 6, with the proviso that when "i" is 0, R^1DAnd R^2DMust be present; r¹And R²Independently represents hydrogen, a hydrocarbyl group or a functional substituent; and R is^1DAnd R^2DWhich are optional and independently represent a deuterium atom or a deuterium-enriched hydrocarbon group containing at least one deuterium atom.

37. The polymer composition of claim 36, wherein X' "is hydrogen or C₁～C₁₀Nitrogen of the alkyl group.

38. The polymer composition of claim 36 wherein the number of repeat units in the composition is from about 100 to about 100,000.

39. The polymer composition of claim 36 wherein the number of repeat units in the composition is from about 500 to about 50,000.

40. The polymer composition of claim 36 wherein the number of repeat units in the composition is from about 1,000 to about 10,000.

41. The polymer composition of claim 36, wherein R^1DAnd R^2DAt least one of which is present and R^1DAnd R^2DIndependently selected from linear or branched C₁～C₁₀Alkyl wherein at least 40% of the hydrogen atoms in the carbon chain backbone are replaced by deuterium.

42. The polymer composition of claim 41, wherein R^1DAnd R^2DAre present.

43. The polymer composition of claim 36, wherein R^1DAnd R^2DAt least one of which is present and R^1DAnd R^2DIndependently selected from linear or branched C₁～C₁₀Alkyl wherein at least 50% of the hydrogen atoms in the carbon chain backbone are replaced by deuterium.

44. The polymer composition of claim 43, wherein R^1DAnd R^2DAre present.

45. The polymer composition of claim 36, wherein R^1DAnd R^2DAt least one of which is present and R^1DAnd R^2DIndependently selected from linear or branched C₁～C₁₀Alkyl wherein at least 60% of the hydrogen atoms in the carbon chain backbone are replaced by deuterium.

46. Polymer group according to claim 36Compound (I) wherein R^1DAnd R^2DAre present.

47. The polymer composition of claim 36, wherein the polymer composition is formed in combination with at least one crosslinking agent.

48. The polymer composition of claim 36, wherein the polymer composition is formed from the combination of (a) one or more monomers according to claim 30 and (B) one or more oligomers derived from the monomers of claim 30.

49. The polymer composition of claim 1, used in a waveguide.

50. The polymer composition of claim 22, used in a waveguide.

51. The polymer composition of claim 36, used in a waveguide.

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